Aromatic compounds, organic semiconductor layers, and organic thin film transistors

Abstract

The object of the present invention is to provide an aromatic compound containing a specific substituent, an organic semiconductor layer and an organic thin film transistor using the same, wherein the aromatic compound containing a specific substituent is a coating-type organic semiconductor material having high carrier mobility, high heat resistance and appropriate solubility. The above-mentioned object is achieved by an aromatic compound represented by the following formula (1-I) or (1-II). In formula (1-I) and (1-II), Ar represents a monocyclic ring, etc., and X 1 , X 2 represents oxygen atoms, etc., Y 1 , Y 2 Represents CR 6 et al., R. 1 ~R 6 represents a hydrogen atom, etc., R 1 ~R 6 At least one of them is a group represented by the following formula (2). In formula (2), A represents a predetermined alkenyl group, l and n represent 0 or 1, m represents an integer from 1 to 20, and Z 1 , Z 2 Represents a hydrogen atom, etc.

Description

Technical Field

[0001] The present invention relates to a novel aromatic compound that can be used as an electronic material such as an organic semiconductor material, an organic semiconductor layer and an organic thin film transistor using the same, and in particular to an aromatic compound having a specific substituent that has excellent solubility and heat resistance and can therefore be applied to various device manufacturing processes, and an organic semiconductor layer and an organic thin film transistor using the same. Background Art

[0002] Organic semiconductor devices, represented by organic thin film transistors, have characteristics that are not found in inorganic semiconductor devices, such as energy saving, low cost, and flexibility, and therefore have attracted attention in recent years. The organic semiconductor device is composed of a variety of materials such as an organic semiconductor layer, a substrate, an insulating layer, and an electrode. Among them, the organic semiconductor layer that is responsible for the carrier migration of the charge has the core function of the device. In addition, the performance of the organic semiconductor device is determined by the carrier mobility of the organic semiconductor material constituting the organic semiconductor layer, so it is expected that an organic semiconductor material that can bring high carrier mobility will appear.

[0003] As a method for manufacturing an organic semiconductor layer, generally known methods include a vacuum evaporation method in which an organic material is vaporized under high temperature and vacuum, a coating method in which an organic material is dissolved in an appropriate solvent and the solution is applied, etc. Among them, the coating method can be implemented even when a printing technique is used without using high temperature and high vacuum conditions, so it can be expected that a significant reduction in the manufacturing cost of device manufacturing can be achieved, and it is an economically preferred process.

[0004] The organic semiconductor material used in such a coating method preferably has a heat resistance of 130°C or higher and a solubility of 0.1 wt% or higher at room temperature from the viewpoint of high carrier mobility and device manufacturing process. Furthermore, in the case of transistors used for electronic paper and organic EL applications, the carrier mobility is preferably 1.0 cm 2 / V·seconds or more.

[0005] Here, generally speaking, it is known that the low-molecular semiconductor of the rod-shaped molecular long axis with condensed ring system has higher crystallinity than high-molecular semiconductor, and therefore easily shows high carrier mobility. However, generally speaking, low-molecular semiconductor has the problem of low solubility. Although it is reported that the semiconductor of alkyl is introduced in order to improve solubility, there is the problem of carrier mobility and heat resistance reduction. In addition, it is reported that the semiconductor of aromatic substituent is introduced in order to utilize π stacking to show high carrier mobility, but it is also reported that the cost of showing high mobility is a significant reduction in solubility. Therefore, at present, the organic semiconductor material of the low-molecular system having high carrier mobility, high heat resistance and appropriate solubility is almost unknown.

[0006] Currently, as low molecular weight materials, 2,7-dialkyl-substituted benzothienobenzothiophene (for example, see Patent Document 1 and Non-Patent Document 1), 2,7-diphenyl[1]benzothieno[3,2-b][1]benzothiophene (for example, see Non-Patent Document 2), dithienyl biphenylene derivatives (for example, see Patent Document 2), etc. have been proposed.

[0007] However, in the case of the dialkyl-substituted benzothienobenzothiophene described in Patent Document 1 and Non-Patent Document 1, there is a problem of heat resistance such that the transistor does not operate when heated to 130° C. or higher.

[0008] 2,7-Diphenyl[1]benzothieno[3,2-b][1]benzothiophene described in Non-Patent Document 2 is generally almost insoluble in organic solvents and has a problem in solubility.

[0009] Furthermore, the alkyl-substituted dithienyl biphenylene derivative described in Patent Document 2 has both high heat resistance and moderate solubility and can be suitably used in organic semiconductors, but compounds having higher carrier mobility are desired.

[0010] Prior art literature

[0011] Patent Literature

[0012] Patent Document 1: WO2008 / 047896

[0013] Patent Document 2: Japanese Patent Application Publication No. 2018 / 174322

[0014] Non-patent literature

[0015] Non-patent document 1: Journal of American Chemical Society, 2007, Vol. 129, pp. 15732-15733

[0016] Non-patent document 2: Journal of American Chemical Society, 2006, Vol. 128, pp. 12604-12605 Summary of the invention

[0017] Technical problem to be solved by the invention

[0018] The present invention has been made in view of the above-mentioned problems, and an object of the present invention is to provide a novel coating-type organic semiconductor material having high carrier mobility, high heat resistance, and appropriate solubility.

[0019] Means for solving technical problems

[0020] The inventors of the present invention conducted intensive studies to solve the above-mentioned technical problems and found that a novel aromatic compound having a specific substituent can form an organic semiconductor material having high heat resistance and appropriate solubility while bringing high carrier mobility, thereby completing the present invention.

[0021] That is, the present invention relates to an aromatic compound represented by any one of the following formula (1-I) or formula (1-II), an organic semiconductor layer containing the aromatic compound, and an organic thin film transistor having the semiconductor layer.

[0022]

Chemistry 1

[0023]

[0024] [(Herein, Ar represents a single ring or a condensed ring of 2 to 6 rings; X 1 , X 2 Each independently represents an oxygen atom, a sulfur atom, a selenium atom, NR 3 , or CR 4 =CR 5 1 of the following; Y 1 , Y 2 Each independently represents CR 6 or any one of nitrogen atoms; R 1 ~R 6 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, a diene group having 4 to 22 carbon atoms, a dialkynyl group having 4 to 22 carbon atoms, an aryl group having 4 to 26 carbon atoms, or a group represented by the following formula (2), R 1 ~R 6 At least one of them is a group represented by the following formula (2).

[0025]

Chemistry 2

[0026]

[0027] (Herein, A represents one selected from an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, or an aryl group having 4 to 26 carbon atoms; l and n each independently represent 0 or 1,

[0028] m represents an integer from 1 to 20; Z 1 , Z 2 When they appear respectively, they are the same or different and represent one selected from a hydrogen atom, a halogen atom, and an alkyl group having 1 to 20 carbon atoms. )]

[0029] Effects of the Invention

[0030] The novel aromatic compound of the present invention has high heat resistance and appropriate solubility while providing high carrier mobility, and therefore can provide an organic thin film transistor exhibiting excellent semiconductor characteristics by coating, and the effect is extremely high. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 is a diagram showing the structure of an organic thin film transistor based on a cross-sectional shape. DETAILED DESCRIPTION

[0032] The present invention is described in detail below.

[0033] The present invention is an aromatic compound represented by any one of the above formula (1-I) or formula (1-II) (hereinafter referred to as "the compound of the present invention").

[0034] Ar in formula (1-I) and formula (1-II) represents a single ring or a condensed ring of 2 to 6 rings. In order to show higher carrier mobility, Ar is preferably a condensed ring of 2 to 4 rings; in order to show higher solubility, it is more preferably a condensed ring of 2 to 3 rings.

[0035] Each ring constituting the monocyclic ring or the condensed ring of 2 to 6 rings is a 4- to 8-membered ring, and is preferably a 4- to 6-membered ring from the viewpoint of easy formation of π stacking.

[0036] Specific examples of the single ring or condensed ring of 2 to 6 rings represented by Ar include single rings such as cyclobutene ring, thiophene ring, furan ring, selenophene ring, thiazole ring, oxazole ring, pyrrole ring, imidazole ring, benzene ring, and pyridine ring; and condensed rings such as thienothiophene ring, naphthalene ring, biphenylene ring, anthracene ring, dithienothiophene ring, dithienothiophene benzo ring, benzothienothiophene ring, tetracene ring, bis(dithienothiophene)benzo ring, and bis(benzothienothiophene)benzo ring. In order to exhibit higher carrier mobility, condensed rings of 2 to 4 rings such as thienothiophene ring, naphthalene ring, biphenylene ring, anthracene ring, dithienothiophene ring, and benzothienothiophene ring are preferred, and condensed rings of 2 to 3 rings such as thienothiophene ring, naphthalene ring, biphenylene ring, and anthracene ring are more preferred.

[0037] X in formula (1-I) and formula (1-II) 1 , X 2 Each independently represents an oxygen atom, a sulfur atom, a selenium atom, NR 3 , or CR 4 =CR 5 In order to make the compound of the present invention show higher stability, X 1 and X 2 At least one of them is preferably a sulfur atom or CR 4 =CR 5 Any of them is more preferably a sulfur atom.

[0038] Y in formula (1-I) and formula (1-II) 1 , Y 2 Each independently represents CR 6 In order to make the compound of the present invention show higher stability, Y 1 and Y 2 At least one of the above is preferably CR 6 .

[0039] R in formula (1-I) and formula (1-II) 1 ~R 6 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, a diene group having 4 to 22 carbon atoms, a dialkynyl group having 4 to 22 carbon atoms, an aryl group having 4 to 26 carbon atoms, or a group represented by formula (2), and R 1 ~R 6 At least one of them is a group represented by formula (2).

[0040] As the R 1 ~R 6 The halogen atom in " represents, for example, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom; from the viewpoint of stability, it is preferably a fluorine atom or a chlorine atom.

[0041] As the R 1 ~R 6 The alkyl group having 1 to 20 carbon atoms in the alkyl group may be a straight chain, branched chain, or cyclic alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an n-pentyl group, an isovaleryl group, an n-hexyl group, an isohexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, an n-dodecyl group, an n-tridecyl group, an n-tetradecyl group, an n-octadecyl group, a 2-ethylhexyl group, a 3-ethylheptyl group, a 3-ethyldecyl group, a 2-hexyldecyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group. Among them, from the viewpoint of forming an aromatic compound having high carrier mobility and high solubility, an alkyl group having 1 to 14 carbon atoms is preferred, and a straight chain alkyl group having 1 to 14 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-dodecyl group, an n-tridecyl group, and an n-tetradecyl group is more preferred.

[0042] As the R 1 ~R 6The alkenyl group having 2 to 20 carbon atoms in the group includes, for example, ethenyl, propenyl, butenyl, 2-methylpropenyl, n-pentenyl, 2-methylbutenyl, n-hexenyl, 2-methylpentenyl, n-heptenyl, n-octenyl, 2-ethylhexenyl, n-nonenyl, 2-ethylheptenyl, n-decenyl, n-dodecenyl, cyclopenten-1-yl, cyclohexen-1-yl and cyclohepten-1-yl.

[0043] As the R 1 ~R 6 Examples of the alkynyl group having 2 to 20 carbon atoms include ethynyl, propynyl, butynyl, n-pentynyl, n-hexynyl, n-heptynyl, n-octynyl, n-nonynyl, n-decynyl and n-dodecynyl.

[0044] As the R 1 ~R 6 The dienyl group having 4 to 22 carbon atoms in the group includes, for example, butadienyl, pentadienyl, hexadienyl, n-heptadienyl, n-octadienyl, n-nonadienyl, n-decadienyl, n-dodecadienyl, n-tridecadienyl and the like, preferably 1,3-dienyl group having 4 to 22 carbon atoms, and more preferably hexa-1,3-dienyl, n-heptadienyl, n-octadienyl, n-non-1,3-dienyl, and n-decadienyl.

[0045] As the R 1 ~R 6 The dialkynyl group having 4 to 22 carbon atoms in the group includes, for example, butadiynyl, pentadiynyl, hexadiynyl, n-heptadiynyl, n-octadiynyl, n-nonadiynyl, n-decadiynyl, n-dodecadiynyl, n-tridecadiynyl and the like, preferably a 1,3-diynyl group having 4 to 22 carbon atoms, and more preferably a hexadiynyl, n-heptadiynyl, n-octadiynyl, n-nonadiynyl, n-decadiynyl, n-dodecadiynyl and n-tridecadiynyl group.

[0046] The R 1 ~R 6The aryl group having 4 to 26 carbon atoms in the formula (a) includes a heteroaryl group having 4 to 24 carbon atoms. Examples of the aryl group having 4 to 26 carbon atoms include phenyl; alkyl-substituted phenyl groups such as p-tolyl, p-(n-hexyl)phenyl, p-(n-octyl)phenyl, and p-(2-ethylhexyl)phenyl; 2-furyl, and 2-thienyl; 5-fluoro-2-furyl, 5-methyl-2-furyl, 5-ethyl-2-furyl, 5-(n-propyl)-2-furyl, 5-(n-butyl)-2-furyl, 5-(n-pentyl)-2-furyl, 5-(n-hexyl)-2- Alkyl-substituted heteroaryl groups include furanyl, 5-(n-octyl)-2-furanyl, 5-(2-ethylhexyl)-2-furanyl, 5-fluoro-2-thienyl, 5-methyl-2-thienyl, 5-ethyl-2-thienyl, 5-(n-propyl)-2-thienyl, 5-(n-butyl)-2-thienyl, 5-(n-pentyl)-2-thienyl, 5-(n-hexyl)-2-thienyl, 5-(n-octyl)-2-thienyl and 5-(2-ethylhexyl)-2-thienyl.

[0047] These R 1 ~R 6 Among them, in view of stability, it is preferably selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 4 to 26 carbon atoms, or a group represented by formula (2); in view of high solubility, it is more preferably selected from a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a group represented by formula (2); from the viewpoint of high carrier mobility, R 1 and R 2 Only one or both of them represent a group represented by formula (2), R 3 ~R 6 A hydrogen atom.

[0048] A in formula (2) represents one selected from an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, or an aryl group having 4 to 26 carbon atoms; in order to exhibit higher carrier mobility, an aryl group having 4 to 26 carbon atoms is more preferred.

[0049] Examples of the alkenyl group having 2 to 20 carbon atoms in the formula (2) include vinyl, propenyl, butenyl, 2-methylpropenyl, n-pentenyl, 2-methylbutenyl, n-hexenyl, 2-methylpentenyl, n-heptenyl, n-octenyl, 2-ethylhexenyl, n-nonenyl, 2-ethylheptenyl, n-decenyl, n-dodecenyl, cyclopenten-1-yl, cyclohexen-1-yl, cyclohepten-1-yl, 2-phenylvinyl, 1-phenylvinyl, 2-(4-methylphenyl)vinyl, and 2-(4-n-butyl)vinyl.

[0050] Examples of the alkynyl group having 2 to 20 carbon atoms in formula (2) include ethynyl, propynyl, butynyl, n-pentynyl, n-hexynyl, n-heptynyl, n-octynyl, n-nonynyl, n-decynyl, n-dodecynyl, 2-phenylethynyl, 1-phenylethynyl, 2-(4-methylphenyl)ethynyl, and 2-(4-n-butyl)ethynyl.

[0051] The aryl group having 4 to 26 carbon atoms in formula (2) includes a heteroaryl group having 4 to 24 carbon atoms. Examples of the aryl group having 4 to 26 carbon atoms include phenyl; p-tolyl, p-ethylphenyl, p-(n-propyl)phenyl, p-(isopropyl)phenyl, p-(n-butyl)phenyl, p-(2-methylpropyl)phenyl, p-(n-pentyl)phenyl, p-(3-methylbutyl)phenyl, p-(n-hexyl)phenyl, p-(4-methylpentyl)phenyl, p-(n-heptyl)phenyl, p-(n-octyl)phenyl, p-(2-ethylhexyl)phenyl, m-ethylphenyl, m-(n-propyl)phenyl, m-(n-butyl)phenyl, m-(2-methylpropyl)phenyl, o-ethylphenyl, o-(n-propyl)phenyl, Alkyl-substituted phenyl groups such as indan-5-yl; alkoxy-substituted phenyl groups such as p-methoxyphenyl, p-ethoxyphenyl, p-(n-propoxy)phenyl, p-(n-butylphenoxy)phenyl, p-(n-pentyloxy)phenyl, p-(n-hexyloxy)phenyl, p-(n-heptyloxy)phenyl, p-(n-octyloxy)phenyl, m-methoxyphenyl, m-(n-propoxy)phenyl, o-methoxyphenyl, o-(n-propoxy)phenyl, 3,4-methylenedioxyphenyl, 3,4-ethylenedioxyphenyl, 2,3-dihydrobenzofuran-5-yl, 2,3-dihydrobenzofuran-6-yl; p-fluorophenyl, m-fluorophenyl, Fluorine-substituted phenyl groups such as o-fluorophenyl, 3,5-difluorophenyl, perfluorophenyl, p-(trifluoromethyl)phenyl, m-(trifluoromethyl)phenyl, and o-(trifluoromethyl)phenyl; 2-furyl, 2-thienyl; 5-fluoro-2-furyl, 5-methyl-2-furyl, 5-ethyl-2-furyl, 5-(n-propyl)-2-furyl, 5-(n-butyl)-2-furyl, 5-(n-pentyl)-2-furyl, 5-(n-hexyl)-2-furyl, 5-(n-octyl)-2-furyl, 5-(2-ethylhexyl)-2-furyl, 5-fluoro-2-thienyl, 5- Alkyl-substituted heteroaryl groups such as methyl-2-thienyl, 5-ethyl-2-thienyl, 5-(n-propyl)-2-thienyl, 5-(n-butyl)-2-thienyl, 5-(n-pentyl)-2-thienyl, 5-(n-hexyl)-2-thienyl, 5-(n-octyl)-2-thienyl, 5-(2-ethylhexyl)-2-thienyl, thieno[3,2-b]thien-2-yl, 5-methylthieno[3,2-b]thien-2-yl, 5-ethylthieno[3,2-b]thien-2-yl, and 5-(n-butyl)thieno[3,2-b]thien-2-yl are more preferred. Among them, phenyl and alkyl-substituted phenyl groups are more preferred from the viewpoint of exhibiting high carrier mobility and high solubility.

[0052] In formula (2), l and n each independently represent 0 or 1. From the perspective of ease of synthesis, n is preferably 0. In order to obtain high carrier mobility, it is more preferred that both l and n are 0.

[0053] In formula (2), m represents an integer of 1 to 20. To obtain high solubility, m is preferably an integer of 1 to 8. To obtain high carrier mobility, m is more preferably an integer of 1 to 4, and even more preferably 2.

[0054] Z in formula (2) 1 , Z 2 When they appear respectively, they are the same or different and represent one of a hydrogen atom, a halogen atom, and an alkyl group having 1 to 20 carbon atoms.

[0055] As the Z 1 , Z 2 The halogen atom in " represents, for example, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom; from the viewpoint of stability, it is preferably a fluorine atom or a chlorine atom.

[0056] As the Z 1 , Z 2 The alkyl group having 1 to 20 carbon atoms in the alkyl group may be a straight chain, branched chain, or cyclic alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an n-pentyl group, an isovaleryl group, an n-hexyl group, an isohexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, an n-dodecyl group, an n-tridecyl group, an n-tetradecyl group, an n-octadecyl group, a 2-ethylhexyl group, a 3-ethylheptyl group, a 3-ethyldecyl group, a 2-hexyldecyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group. Among them, from the viewpoint of forming an aromatic compound showing high carrier mobility and high solubility, an alkyl group having 1 to 8 carbon atoms is preferred, and a methyl group, an ethyl group, and an n-propyl group are further preferred.

[0057] In order to obtain high carrier mobility, the Z 1 , Z 2 It is preferably a hydrogen atom or a halogen atom, and more preferably a hydrogen atom.

[0058] In formula (2), preferably, A is phenyl or alkyl-substituted phenyl, l and n are both 0, m is an integer from 1 to 4, and Z 1 , Z 2 is any one of a hydrogen atom and a halogen atom. Thus, the compound of the present invention exhibits higher carrier mobility.

[0059] In order to obtain high carrier mobility, the group represented by formula (2) is preferably 2-phenylethyl or 2-alkyl-substituted phenylethyl. In order to obtain high heat resistance and high solubility, it is further preferably 2-phenylethyl, 2-(4-methylphenyl)ethyl, 2-(4-ethylphenyl)ethyl, 2-(4-n-propylphenyl)ethyl, 2-(4-n-butylphenyl)ethyl, 2-(4-n-pentylphenyl)ethyl, 2-(4-n-hexylphenyl)ethyl, 2-(4-n-heptylphenyl)ethyl, 2-(4-n-octylphenyl)ethyl, 2-(4-n-nonylphenyl)ethyl, and 2-(4-n-decylphenyl)ethyl. It is more preferably 2-phenylethyl, 2-(4-n-propylphenyl)ethyl, 2-(4-n-butylphenyl)ethyl, 2-(4-n-pentylphenyl)ethyl, 2-(4-n-hexylphenyl)ethyl, and 2-(4-n-heptylphenyl)ethyl.

[0060] From the viewpoint of ease of synthesis, the aromatic compound of formula (1-I) or (1-II) is preferably an aromatic compound represented by one of the following formulas (3-1) to (3-6).

[0061]

Chemistry 3

[0062]

[0063] [(Here, X 3 , X 4 , X 5 Each independently represents an oxygen atom, a sulfur atom, a selenium atom, a single bond, NR 17 , or CR 18 =CR 19 1 of the 7 ~R 10 Among the combinations of two adjacent components, only one group constitutes the following formula (4), in which R 11 ~R 14 Among the combinations of two adjacent groups, only one group constitutes the following formula (4-2), respectively forming a 5- or 6-membered ring; R that does not constitute the following formula (4) and the following formula (4-2) 7 ~R 14 and R 15 ~R 19 Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, a diene group having 4 to 22 carbon atoms, a dialkynyl group having 4 to 22 carbon atoms, an aryl group having 4 to 26 carbon atoms, or one of the groups represented by the above formula (2).

[0064]

Chemistry 4

[0065]

[0066] (Here, X 6 Represents oxygen atoms, sulfur atoms, selenium atoms, CR 21 =CR 22 , or NR 23 1 of the following; Y 3 Represents CR 24 or any one of nitrogen atoms; R 21 ~R 24 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, a dienyl group having 4 to 22 carbon atoms, a dialkynyl group having 4 to 22 carbon atoms, an aryl group having 4 to 26 carbon atoms, or one of the groups represented by the above formula (2); R 20 is a group represented by the above formula (2).

[0067]

Chemistry 5

[0068]

[0069] (Here, X 6 , Y 3 , R 21 ~R 24 represents X in the above formula (4) 6 , Y 3 , R 21 ~R 24 Same meaning, R 20b represents one selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, a dienyl group having 4 to 22 carbon atoms, a dialkynyl group having 4 to 22 carbon atoms, an aryl group having 4 to 26 carbon atoms, or a group represented by the above formula (2). )]

[0070] In formulas (3-1) to (3-6), R 7 ~R 10 Among the combinations of two adjacent components, only one group constitutes the above formula (4), and in the combination of R 11 ~R 14 Among the combinations of two adjacent components, only one of them constitutes the above formula (4-2), and each forms a 5- or 6-membered ring.

[0071] R that does not constitute formula (4) and formula (4-2) 7 ~R 14 , R 15 ~R 19 , R in formula (4) and formula (4-2) 21 ~R 24Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, a dienyl group having 4 to 22 carbon atoms, a dialkynyl group having 4 to 22 carbon atoms, an aryl group having 4 to 26 carbon atoms, or a group represented by formula (2).

[0072] R 20 It is a group represented by formula (2).

[0073] R 20b It is a group selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, a dienyl group having 4 to 22 carbon atoms, a dialkynyl group having 4 to 22 carbon atoms, an aryl group having 4 to 26 carbon atoms, or a group represented by formula (2). From the viewpoint of achieving high mobility, it is preferably a hydrogen atom, a fluorine atom, or a group represented by formula (2).

[0074] Among the compounds represented by one of formulae (3-1) to (3-6), formula (4-2) is preferably the following formula (4-3).

[0075]

Chemistry 6

[0076]

[0077] (Here, X 6 , Y 3 , R 21 ~R 24 represents X in the above formula (4) 6 , Y 3 , R 21 ~R 24 The same meaning, R 20c represents one selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, a dienyl group having 4 to 22 carbon atoms, a dialkynyl group having 4 to 22 carbon atoms, or an aryl group having 4 to 26 carbon atoms.)

[0078] R 20c It is one selected from a group represented by a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, a dienyl group having 4 to 22 carbon atoms, a dialkynyl group having 4 to 22 carbon atoms, or an aryl group having 4 to 26 carbon atoms, and from the viewpoint of achieving high mobility, it is preferably a hydrogen atom or a fluorine atom, and more preferably a hydrogen atom.

[0079] Among the compounds represented by one of formulae (3-1) to (3-6), formula (4-2) is preferably the following formula (4-4).

[0080]

Chemistry 7

[0081]

[0082] (Here, X 6 , Y 3 , R 21 ~R 24 represents X in the above formula (4) 6 , Y 3 , R 21 ~R 24 The same meaning, R 20d is a group represented by the above formula (2).

[0083] The definition of the group represented by the formula (2) in the formulae (3-1) to (3-6) is the same as the definition of the formula (2) in the above-mentioned formulae (1-I) and (1-II).

[0084] As the R 7 ~R 19 , R 21 ~R 24 , R 20b , R 20c The halogen atom in " represents, for example, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and is preferably a fluorine atom or a chlorine atom from the viewpoint of stability.

[0085] As the R 7 ~R 19 , R 21 ~R 24 , R 20b , R 20c The alkyl group having 1 to 20 carbon atoms in the alkyl group may be a straight chain, branched chain, or cyclic alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an n-pentyl group, an isovaleryl group, an n-hexyl group, an isohexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, an n-dodecyl group, an n-tridecyl group, an n-tetradecyl group, an n-octadecyl group, a 2-ethylhexyl group, a 3-ethylheptyl group, a 3-ethyldecyl group, a 2-hexyldecyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group. Among them, from the viewpoint of forming an aromatic compound having high carrier mobility and high solubility, an alkyl group having 1 to 14 carbon atoms is preferred, and a straight chain alkyl group having 1 to 14 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-dodecyl group, an n-tridecyl group, and an n-tetradecyl group is more preferred.

[0086] As the R 7 ~R 24The alkenyl group having 2 to 20 carbon atoms in the group includes, for example, ethenyl, propenyl, butenyl, 2-methylpropenyl, n-pentenyl, 2-methylbutenyl, n-hexenyl, 2-methylpentenyl, n-heptenyl, n-octenyl, 2-ethylhexenyl, n-nonenyl, 2-ethylheptenyl, n-decenyl, n-dodecenyl, cyclopenten-1-yl, cyclohexen-1-yl and cyclohepten-1-yl.

[0087] As the R 7 ~R 19 , R 21 ~R 24 , R 20b , R 20c Examples of the alkynyl group having 2 to 20 carbon atoms include ethynyl, propynyl, butynyl, n-pentynyl, n-hexynyl, n-heptynyl, n-octynyl, n-nonynyl, n-decynyl and n-dodecynyl.

[0088] As the R 7 ~R 19 , R 21 ~R 24 , R 20b , R 20c The dienyl group having 4 to 22 carbon atoms in the group includes, for example, butadienyl, pentadienyl, hexadienyl, n-heptadienyl, n-octadienyl, n-nonadienyl, n-decadienyl, n-dodecadienyl, n-tridecadienyl and the like, preferably 1,3-dienyl group having 4 to 22 carbon atoms, and more preferably hexa-1,3-dienyl, n-heptadienyl, n-octadienyl, n-non-1,3-dienyl, and n-decadienyl.

[0089] As the R 7 ~R 19 , R 21 ~R 24 , R 20b , R 20c The dialkynyl group having 4 to 22 carbon atoms in the group includes, for example, butadiynyl, pentadiynyl, hexadiynyl, n-heptadiynyl, n-octadiynyl, n-nonadiynyl, n-decadiynyl, n-dodecadiynyl, n-tridecadiynyl and the like, preferably a 1,3-diynyl group having 4 to 22 carbon atoms, and more preferably a hexadiynyl, n-heptadiynyl, n-octadiynyl, n-nonadiynyl, n-decadiynyl, n-dodecadiynyl and n-tridecadiynyl group.

[0090] The R 7 ~R 19 , R 21 ~R 24 , R 20b , R 20cThe aryl group having 4 to 26 carbon atoms in the formula (a) includes a heteroaryl group having 4 to 24 carbon atoms. Examples of the aryl group having 4 to 26 carbon atoms include phenyl; alkyl-substituted phenyl groups such as p-tolyl, p-(n-hexyl)phenyl, p-(n-octyl)phenyl, and p-(2-ethylhexyl)phenyl; 2-furyl, and 2-thienyl; 5-fluoro-2-furyl, 5-methyl-2-furyl, 5-ethyl-2-furyl, 5-(n-propyl)-2-furyl, 5-(n-butyl)-2-furyl, 5-(n-pentyl)-2-furyl, 5-(n-hexyl)-2- Alkyl-substituted heteroaryl groups include furanyl, 5-(n-octyl)-2-furanyl, 5-(2-ethylhexyl)-2-furanyl, 5-fluoro-2-thienyl, 5-methyl-2-thienyl, 5-ethyl-2-thienyl, 5-(n-propyl)-2-thienyl, 5-(n-butyl)-2-thienyl, 5-(n-pentyl)-2-thienyl, 5-(n-hexyl)-2-thienyl, 5-(n-octyl)-2-thienyl and 5-(2-ethylhexyl)-2-thienyl.

[0091] Considering the stability, the R 7 ~R 19 It is preferably a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 4 to 26 carbon atoms, or a group represented by formula (2); in order to achieve high solubility, a hydrogen atom or an alkyl group having 1 to 20 carbon atoms is more preferred.

[0092] Considering the stability, the R 21 ~R 24 Preferably, it is one selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 4 to 26 carbon atoms, or a group represented by formula (2); in order to achieve high carrier mobility, R 21 ~R 24 More preferably, it is one selected from the group consisting of a hydrogen atom and a methyl group, and even more preferably, it is a hydrogen atom.

[0093] X in formulas (3-1) to (3-6) 3 , X 4 , X 5 Represents oxygen atom, sulfur atom, selenium atom, single bond, NR 17 , or CR 18 =CR 19 In order to achieve high carrier mobility, preferably a sulfur atom, a single bond, or CR 18 =CR 19 Any one of the above, more preferably a sulfur atom or CR 18 =CR 19 , and further more preferably a sulfur atom.

[0094] X in formula (4) and (4-2) to (4-3) 6 Represents oxygen atoms, sulfur atoms, selenium atoms, CR 21 =CR 22 , or NR 23 In order to achieve high carrier mobility, preferably a sulfur atom or CR 21 =CR 22 , more preferably a sulfur atom.

[0095] Y in formula (4) and (4-2) to (4-3) 3 Represents CR 24 or nitrogen atoms; considering stability, CR is preferred 24 .

[0096] In order to achieve high carrier mobility, the aromatic compounds represented by formulae (3-1) to (3-6) preferably have a point-symmetric or axisymmetric structure, and more preferably have a point-symmetric structure.

[0097] In order to achieve high solubility and high heat resistance, among the aromatic compounds represented by formulae (3-1) to (3-6), formula (3-1) or formula (3-2) is preferred.

[0098] Furthermore, the aromatic compound represented by the formula (1-I) or the formula (1-II) is preferably an aromatic compound represented by the following formula (5) or the following formula (5-2).

[0099]

Chemistry 8

[0100]

[0101] [(Here, in the 25 ~R 28 Among the combinations of two adjacent components, only one group constitutes the following formula (6), and in the combination of R 29 ~R 32 Among the combinations of two adjacent groups, only one group constitutes the following formula (6-2), respectively forming a 5- or 6-membered ring; R that does not constitute the following formula (6) and the following formula (6-2) 25 ~R 32 and R 69 , R 70 Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, a diene group having 4 to 22 carbon atoms, a dialkynyl group having 4 to 22 carbon atoms, an aryl group having 4 to 26 carbon atoms, or one of the groups represented by the above formula (2).

[0102]

Chemistry 9

[0103]

[0104] (Here, X 7 Represents oxygen atoms, sulfur atoms, selenium atoms, CR 34 =CR 35 , or NR 36 ; Y 4 Represents CR 37 or any one of nitrogen atoms; R 34 ~R 37 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, a dienyl group having 4 to 22 carbon atoms, a dialkynyl group having 4 to 22 carbon atoms, an aryl group having 4 to 26 carbon atoms, or a group represented by the above formula (2), and R 33 is a group represented by the above formula (2).

[0105]

Chemistry 10

[0106]

[0107] (Here, X 7 , Y 4 , R 34 ~R 37 represents X in the above formula (6) 7 , Y 4 , R 34 ~R 37 The same meaning, R 33b represents one selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, a dienyl group having 4 to 22 carbon atoms, a dialkynyl group having 4 to 22 carbon atoms, an aryl group having 4 to 26 carbon atoms, or a group represented by the above formula (2). )]

[0108] In formula (5) and (5-2), R 25 ~R 28 Among the combinations of two adjacent components, only one group constitutes the above formula (6), and in the combination of R 29 ~R 32 Among the combinations of two adjacent components, only one of them constitutes the above formula (6-2), and each forms a 5- or 6-membered ring.

[0109] R that does not constitute formula (6) and formula (6-2) 25 ~R 32 and R 69 , R 70 , R in formula (6) and formula (6-2) 34 ~R 37Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, a dienyl group having 4 to 22 carbon atoms, a dialkynyl group having 4 to 22 carbon atoms, an aryl group having 4 to 26 carbon atoms, or a group represented by formula (2).

[0110] R 33 It is a group represented by formula (2).

[0111] R 33b It is a group selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, a dienyl group having 4 to 22 carbon atoms, a dialkynyl group having 4 to 22 carbon atoms, an aryl group having 4 to 26 carbon atoms, or a group represented by formula (2). From the viewpoint of high mobility, it is preferably a group selected from a hydrogen atom, a fluorine atom, and a group represented by formula (2).

[0112] Among the aromatic compounds represented by formula (5) or formula (5-2), formula (6-2) is preferably the following formula (6-3).

[0113]

Chemistry 11

[0114]

[0115] (Here, X 7 , Y 4 , R 34 ~R 37 represents X in the above formula (6) 7 , Y 4 , R 34 ~R 37 The same meaning, R 33c represents one selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, a diene group having 4 to 22 carbon atoms, a dialkynyl group having 4 to 22 carbon atoms, or an aryl group having 4 to 26 carbon atoms.

[0116] R 33c It is one selected from a group represented by a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, a dienyl group having 4 to 22 carbon atoms, a dialkynyl group having 4 to 22 carbon atoms, or an aryl group having 4 to 26 carbon atoms, and from the viewpoint of high mobility, a hydrogen atom or a fluorine atom is preferred, and a hydrogen atom is more preferred.

[0117] Among the aromatic compounds represented by formula (5) or formula (5-2), formula (6-2) is also preferably the following formula (6-4).

[0118]

Chemistry 12

[0119]

[0120] (Here, X 7 , Y 4 , R 34 ~R 37 represents X in the above formula (6) 7 , Y 4 , R 34 ~R 37 The same meaning, R 33d is a group represented by the above formula (2).

[0121] The definition of the group represented by the formula (2) in the formula (5) and the formula (5-2) is the same as the definition of the formula (2) in the above-mentioned formula (1-I) and the formula (1-II).

[0122] As the R 25 ~R 32 , R 34 ~R 37 , R 69 , R 70 , R 33b , R 33c The halogen atom in " represents, for example, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and is preferably a fluorine atom or a chlorine atom from the viewpoint of stability.

[0123] As the R 25 ~R 32 , R 34 ~R 37 , R 69 , R 70 , R 33b , R 33c The alkyl group having 1 to 20 carbon atoms in the alkyl group may be a straight chain, branched chain, or cyclic alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an n-pentyl group, an isovaleryl group, an n-hexyl group, an isohexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, an n-dodecyl group, an n-tridecyl group, an n-tetradecyl group, an n-octadecyl group, a 2-ethylhexyl group, a 3-ethylheptyl group, a 3-ethyldecyl group, a 2-hexyldecyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group. Among them, from the viewpoint of forming an aromatic compound having high carrier mobility and high solubility, an alkyl group having 1 to 14 carbon atoms is preferred, and a straight chain alkyl group having 1 to 14 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-dodecyl group, an n-tridecyl group, and an n-tetradecyl group is more preferred.

[0124] As the R 25 ~R 32 , R 34 ~R 37 , R 69 , R 70 , R 33b , R 33c The alkenyl group having 2 to 20 carbon atoms in the group includes, for example, ethenyl, propenyl, butenyl, 2-methylpropenyl, n-pentenyl, 2-methylbutenyl, n-hexenyl, 2-methylpentenyl, n-heptenyl, n-octenyl, 2-ethylhexenyl, n-nonenyl, 2-ethylheptenyl, n-decenyl, n-dodecenyl, cyclopenten-1-yl, cyclohexen-1-yl and cyclohepten-1-yl.

[0125] As the R 25 ~R 32 , R 34 ~R 37 , R 69 , R 70 , R 33b , R 33c Examples of the alkynyl group having 2 to 20 carbon atoms include ethynyl, propynyl, butynyl, n-pentynyl, n-hexynyl, n-heptynyl, n-octynyl, n-nonynyl, n-decynyl and n-dodecynyl.

[0126] As the R 25 ~R 32 , R 34 ~R 37 , R 69 , R 70 , R 33b , R 33c The dienyl group having 4 to 22 carbon atoms in the group includes, for example, butadienyl, pentadienyl, hexadienyl, n-heptadienyl, n-octadienyl, n-nonadienyl, n-decadienyl, n-dodecadienyl, n-tridecadienyl and the like, preferably 1,3-dienyl group having 4 to 22 carbon atoms, and more preferably hexa-1,3-dienyl, n-heptadienyl, n-octadienyl, n-non-1,3-dienyl, and n-decadienyl.

[0127] As the R 25 ~R 32 , R 34 ~R 37 , R 69 , R 70 , R 33b , R 33cThe dialkynyl group having 4 to 22 carbon atoms in the group includes, for example, butadiynyl, pentadiynyl, hexadiynyl, n-heptadiynyl, n-octadiynyl, n-nonadiynyl, n-decadiynyl, n-dodecadiynyl, n-tridecadiynyl and the like, preferably a 1,3-diynyl group having 4 to 22 carbon atoms, and more preferably a hexadiynyl, n-heptadiynyl, n-octadiynyl, n-nonadiynyl, n-decadiynyl, n-dodecadiynyl and n-tridecadiynyl group.

[0128] The R 25 ~R 32 , R 34 ~R 37 , R 69 , R 70 , R 33b , R 33c The aryl group having 4 to 26 carbon atoms in the formula (a) includes a heteroaryl group having 4 to 24 carbon atoms. Examples of the aryl group having 4 to 26 carbon atoms include phenyl; alkyl-substituted phenyl groups such as p-tolyl, p-(n-hexyl)phenyl, p-(n-octyl)phenyl, and p-(2-ethylhexyl)phenyl; 2-furyl, and 2-thienyl; 5-fluoro-2-furyl, 5-methyl-2-furyl, 5-ethyl-2-furyl, 5-(n-propyl)-2-furyl, 5-(n-butyl)-2-furyl, 5-(n-pentyl)-2-furyl, 5-(n-hexyl)-2- Alkyl-substituted heteroaryl groups include furanyl, 5-(n-octyl)-2-furanyl, 5-(2-ethylhexyl)-2-furanyl, 5-fluoro-2-thienyl, 5-methyl-2-thienyl, 5-ethyl-2-thienyl, 5-(n-propyl)-2-thienyl, 5-(n-butyl)-2-thienyl, 5-(n-pentyl)-2-thienyl, 5-(n-hexyl)-2-thienyl, 5-(n-octyl)-2-thienyl and 5-(2-ethylhexyl)-2-thienyl.

[0129] Considering the stability, the R 25 ~R 32 , R 69 , R 70 It is preferably a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 4 to 26 carbon atoms, or a group represented by formula (2); in order to achieve high solubility, it is more preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and further preferably one selected from a hydrogen atom and a methyl group.

[0130] Considering the stability, the R 34 ~R 37It is preferably one selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 4 to 26 carbon atoms, or a group represented by formula (2); in order to achieve high carrier mobility, it is more preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a group represented by formula (2), and R is further preferably 34 ~R 37 A hydrogen atom.

[0131] X in formula (6) and (6-2) to (6-4) 7 Represents oxygen atoms, sulfur atoms, selenium atoms, CR 34 =CR 35 , or NR 36 ; In order to achieve high solubility, sulfur atoms, oxygen atoms, sulfur atoms, and selenium atoms are preferred; in order to achieve high carrier mobility, sulfur atoms are further preferred.

[0132] Y in formula (6) and (6-2) to (6-4) 4 Represents CR 37 or nitrogen atom, preferably CR considering stability 37 .

[0133] In order to achieve high carrier mobility, the aromatic compounds represented by Formula (5) and Formula (5-2) preferably have a point-symmetric or axisymmetric structure, and more preferably have a point-symmetric structure.

[0134] In order to achieve high solubility, the aromatic compound represented by the formula (5) is preferred among the aromatic compounds represented by the formula (5) and the formula (5-2).

[0135] In addition, from the viewpoint of ease of synthesis, the aromatic compound represented by the formula (5) or the formula (5-2) is preferably one compound selected from the following formulas (7-1) to (7-5).

[0136]

Chemistry 13

[0137]

[0138] (Here, X 8 , X 9 Each independently represents an oxygen atom, a sulfur atom, a selenium atom, or NR 44 1 of the following; Y 5 , Y 6 Each independently represents CR 45 or any one of nitrogen atoms; R 38 ~R 45 , R 71 , R 72each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, a diene group having 4 to 22 carbon atoms, a dialkynyl group having 4 to 22 carbon atoms, an aryl group having 4 to 26 carbon atoms, or a group represented by formula (2), and R 38 ~R 45 At least one of them is a group represented by formula (2), R 38 and R 41 At least one of them is a group represented by formula (2).

[0139] X in formulas (7-1) to (7-5) 8 , X 9 Each independently represents an oxygen atom, a sulfur atom, a selenium atom, NR 44 Considering the stability, preferably a sulfur atom, an oxygen atom, a sulfur atom, a selenium atom; in order to achieve high carrier mobility, a sulfur atom is further preferably used.

[0140] Y in formulas (7-1) to (7-5) 5 , Y 6 Each independently represents CR 45 or nitrogen atoms; considering stability, CR is preferred 45 .

[0141] R in formula (7-1) to (7-5) 38 ~R 45 , R 71 , R 72 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, a diene group having 4 to 22 carbon atoms, a dialkynyl group having 4 to 22 carbon atoms, an aryl group having 4 to 26 carbon atoms, or a group represented by the above formula (2), and R 38 ~R 45 At least one of them is a group represented by the above formula (2).

[0142] R in formula (7-1) to (7-5) 38 , R 41 Only one or both of them are groups represented by formula (2).

[0143] The definition of the group represented by the formula (2) in the formulas (7-1) to (7-5) is the same as the definition of the formula (2) in the above-mentioned formulas (1-I) and (1-II).

[0144] As the R 38 ~R 45 , R 71 , R 72The halogen atom in " represents, for example, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and is preferably a fluorine atom or a chlorine atom from the viewpoint of stability.

[0145] As the R 38 ~R 45 , R 71 , R 72 The alkyl group having 1 to 20 carbon atoms in the alkyl group may be a linear, branched, or cyclic alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an n-pentyl group, an isovaleryl group, an n-hexyl group, an isohexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, an n-dodecyl group, an n-tridecyl group, an n-tetradecyl group, an n-octadecyl group, a 2-ethylhexyl group, a 3-ethylheptyl group, a 3-ethyldecyl group, a 2-hexyldecyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group. Among them, from the viewpoint of forming an aromatic compound having high carrier mobility and high solubility, an alkyl group having 1 to 14 carbon atoms is preferred, and a linear alkyl group having 1 to 14 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-dodecyl group, an n-tridecyl group, and an n-tetradecyl group is more preferred.

[0146] As the R 38 ~R 45 , R 71 , R 72 The alkenyl group having 2 to 20 carbon atoms in the group includes, for example, ethenyl, propenyl, butenyl, 2-methylpropenyl, n-pentenyl, 2-methylbutenyl, n-hexenyl, 2-methylpentenyl, n-heptenyl, n-octenyl, 2-ethylhexenyl, n-nonenyl, 2-ethylheptenyl, n-decenyl, n-dodecenyl, cyclopenten-1-yl, cyclohexen-1-yl and cyclohepten-1-yl.

[0147] As the R 38 ~R 45 , R 71 , R 72 Examples of the alkynyl group having 2 to 20 carbon atoms include ethynyl, propynyl, butynyl, n-pentynyl, n-hexynyl, n-heptynyl, n-octynyl, n-nonynyl, n-decynyl and n-dodecynyl.

[0148] As the R 38 ~R 45 , R 71 , R 72The dienyl group having 4 to 22 carbon atoms in the group includes, for example, butadienyl, pentadienyl, hexadienyl, n-heptadienyl, n-octadienyl, n-nonadienyl, n-decadienyl, n-dodecadienyl, n-tridecadienyl and the like, preferably 1,3-dienyl group having 4 to 22 carbon atoms, and more preferably hexa-1,3-dienyl, n-heptadienyl, n-octadienyl, n-non-1,3-dienyl, and n-decadienyl.

[0149] As the R 38 ~R 45 , R 71 , R 72 The dialkynyl group having 4 to 22 carbon atoms in the group includes, for example, butadiynyl, pentadiynyl, hexadiynyl, n-heptadiynyl, n-octadiynyl, n-nonadiynyl, n-decadiynyl, n-dodecadiynyl, n-tridecadiynyl and the like, preferably a 1,3-diynyl group having 4 to 22 carbon atoms, and more preferably a hexadiynyl, n-heptadiynyl, n-octadiynyl, n-nonadiynyl, n-decadiynyl, n-dodecadiynyl and n-tridecadiynyl group.

[0150] The R 38 ~R 45 , R 71 , R 72 The aryl group having 4 to 26 carbon atoms in the formula (a) includes a heteroaryl group having 4 to 24 carbon atoms. Examples of the aryl group having 4 to 26 carbon atoms include phenyl; alkyl-substituted phenyl groups such as p-tolyl, p-(n-hexyl)phenyl, p-(n-octyl)phenyl, and p-(2-ethylhexyl)phenyl; 2-furyl, and 2-thienyl; 5-fluoro-2-furyl, 5-methyl-2-furyl, 5-ethyl-2-furyl, 5-(n-propyl)-2-furyl, 5-(n-butyl)-2-furyl, 5-(n-pentyl)-2-furyl, 5-(n-hexyl)-2- Alkyl-substituted heteroaryl groups include furanyl, 5-(n-octyl)-2-furanyl, 5-(2-ethylhexyl)-2-furanyl, 5-fluoro-2-thienyl, 5-methyl-2-thienyl, 5-ethyl-2-thienyl, 5-(n-propyl)-2-thienyl, 5-(n-butyl)-2-thienyl, 5-(n-pentyl)-2-thienyl, 5-(n-hexyl)-2-thienyl, 5-(n-octyl)-2-thienyl and 5-(2-ethylhexyl)-2-thienyl.

[0151] Considering the stability, the R 38 ~R 45 , R 71 , R 72It is preferably one selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 4 to 26 carbon atoms, or a group represented by formula (2); in order to achieve high solubility, it is more preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a group represented by formula (2). From the viewpoint of high carrier mobility, R 38 , R 41 It is preferably one selected from the group represented by the above formula (2), a hydrogen atom, and a fluorine atom, more preferably one selected from the group represented by the above formula (2) and a hydrogen atom, and further preferably R 38 and R 41 Both are groups represented by the above formula (2). 39 , R 40 , R 42 ~R 45 , R 71 , R 72 More preferably, it is one selected from the group consisting of a hydrogen atom and a methyl group, and still more preferably, it is a hydrogen atom.

[0152] In order to obtain high carrier mobility, the aromatic compounds represented by the above formulae (7-1) to (7-5) preferably have a point-symmetric or axisymmetric structure, and more preferably have a point-symmetric structure.

[0153] Among formulas (7-1) to (7-5), in order to achieve high solubility, any one of formula (7-1), (7-2) or (7-5) is preferred; in order to achieve high carrier mobility, formula (7-1) is more preferred.

[0154] In addition to the above-mentioned formulas (7-1) to (7-5), the more preferred compound structure of the compound of the present invention can also be represented by one of the following formulas (8-1) to (8-11). Among these, from the viewpoint of high heat resistance and high solubility, it is preferably an aromatic compound selected from (7-1) to (7-5) and (8-2) to (8-9) in which the number of condensed rings is 4 to 5, and from the viewpoint of high carrier mobility, it is more preferably an aromatic compound selected from the formulas (7-1) to (7-5), (8-2) to (8-3), and (8-5) to (8-8) in which the structure is point-symmetrical.

[0155]

Chemistry 14

[0156]

[0157] (Here, X represents an oxygen atom, a sulfur atom, a selenium atom, NR 58 , or CR 59 =CR 60 One of the following; Y indicates CR 61 or any one of nitrogen atoms; R46 ~R 61 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, a diene group having 4 to 22 carbon atoms, a dialkynyl group having 4 to 22 carbon atoms, an aryl group having 4 to 26 carbon atoms, or a group represented by formula (2), and R 46 ~R 61 At least one of them is a group represented by formula (2), R 46 and R 47 At least one of them is a group represented by formula (2); o represents 0 or 1. )

[0158] In formulas (8-1) to (8-11), X represents an oxygen atom, a sulfur atom, a selenium atom, NR 58 , or CR 59 =CR 60 Considering the stability, it is preferably one of an oxygen atom, a sulfur atom, and a selenium atom; in order to achieve high carrier mobility, a sulfur atom is further preferably selected.

[0159] In formulas (8-1) to (8-11), Y represents CR 61 or nitrogen atoms; considering stability, CR is preferred 61 .

[0160] R in formulas (8-1) to (8-11) 46 ~R 61 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, a diene group having 4 to 22 carbon atoms, a dialkynyl group having 4 to 22 carbon atoms, an aryl group having 4 to 26 carbon atoms, or a group represented by formula (2), and R 46 ~R 61 At least one of them is a group represented by formula (2).

[0161] In addition, the definition of the group represented by formula (2) in formulas (8-1) to (8-11) has the same meaning as that of the above-mentioned formula (1-I) and formula (1-II).

[0162] As the R 46 ~R 61 The halogen atom in " represents, for example, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom; from the viewpoint of stability, it is preferably a fluorine atom or a chlorine atom.

[0163] As the R 46 ~R 61The alkyl group having 1 to 20 carbon atoms in the alkyl group may be a linear, branched, or cyclic alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an n-pentyl group, an isovaleryl group, an n-hexyl group, an isohexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, an n-dodecyl group, an n-tridecyl group, an n-tetradecyl group, an n-octadecyl group, a 2-ethylhexyl group, a 3-ethylheptyl group, a 3-ethyldecyl group, a 2-hexyldecyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group. Among them, from the viewpoint of forming an aromatic compound having high carrier mobility and high solubility, an alkyl group having 1 to 14 carbon atoms is preferred, and a linear alkyl group having 1 to 14 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-dodecyl group, an n-tridecyl group, and an n-tetradecyl group is more preferred.

[0164] As the R 46 ~R 61 The alkenyl group having 2 to 20 carbon atoms in the group includes, for example, ethenyl, propenyl, butenyl, 2-methylpropenyl, n-pentenyl, 2-methylbutenyl, n-hexenyl, 2-methylpentenyl, n-heptenyl, n-octenyl, 2-ethylhexenyl, n-nonenyl, 2-ethylheptenyl, n-decenyl, n-dodecenyl, cyclopenten-1-yl, cyclohexen-1-yl and cyclohepten-1-yl.

[0165] As the R 46 ~R 61 Examples of the alkynyl group having 2 to 20 carbon atoms include ethynyl, propynyl, butynyl, n-pentynyl, n-hexynyl, n-heptynyl, n-octynyl, n-nonynyl, n-decynyl and n-dodecynyl.

[0166] As the R 46 ~R 61 The dienyl group having 4 to 22 carbon atoms in the group includes, for example, butadienyl, pentadienyl, hexadienyl, n-heptadienyl, n-octadienyl, n-nonadienyl, n-decadienyl, n-dodecadienyl, n-tridecadienyl and the like, preferably 1,3-dienyl group having 4 to 22 carbon atoms, and more preferably hexa-1,3-dienyl, n-heptadienyl, n-octadienyl, n-non-1,3-dienyl, and n-decadienyl.

[0167] As the R 46 ~R 61The dialkynyl group having 4 to 22 carbon atoms in the group includes, for example, butadiynyl, pentadiynyl, hexadiynyl, n-heptadiynyl, n-octadiynyl, n-nonadiynyl, n-decadiynyl, n-dodecadiynyl, n-tridecadiynyl and the like, preferably a 1,3-diynyl group having 4 to 22 carbon atoms, and more preferably a hexadiynyl, n-heptadiynyl, n-octadiynyl, n-nonadiynyl, n-decadiynyl, n-dodecadiynyl and n-tridecadiynyl group.

[0168] The R 46 ~R 61 The aryl group having 4 to 26 carbon atoms in the formula (a) includes a heteroaryl group having 4 to 24 carbon atoms. Examples of the aryl group having 4 to 26 carbon atoms include phenyl; alkyl-substituted phenyl groups such as p-tolyl, p-(n-hexyl)phenyl, p-(n-octyl)phenyl, and p-(2-ethylhexyl)phenyl; 2-furyl, and 2-thienyl; 5-fluoro-2-furyl, 5-methyl-2-furyl, 5-ethyl-2-furyl, 5-(n-propyl)-2-furyl, 5-(n-butyl)-2-furyl, 5-(n-pentyl)-2-furyl, 5-(n-hexyl)-2- Alkyl-substituted heteroaryl groups include furanyl, 5-(n-octyl)-2-furanyl, 5-(2-ethylhexyl)-2-furanyl, 5-fluoro-2-thienyl, 5-methyl-2-thienyl, 5-ethyl-2-thienyl, 5-(n-propyl)-2-thienyl, 5-(n-butyl)-2-thienyl, 5-(n-pentyl)-2-thienyl, 5-(n-hexyl)-2-thienyl, 5-(n-octyl)-2-thienyl and 5-(2-ethylhexyl)-2-thienyl.

[0169] Considering the stability, the R 46 ~R 61 Preferably, it is one selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 4 to 26 carbon atoms, or a group represented by formula (2). 46 and R 47 More preferably, it is one of the group represented by formula (2), a hydrogen atom, and a fluorine atom. More preferably, it is one of the group represented by formula (2), a hydrogen atom. More preferably, R 46 and R 47 Both are groups represented by formula (2). 48 ~R 61 It is preferably one selected from a hydrogen atom and a methyl group, and more preferably a hydrogen atom.

[0170] o in formulas (8-5) and (8-6) represents 0 or 1; in order to achieve high carrier mobility, it is preferably 1.

[0171] As specific examples of the compounds of the present invention, the following substances can be cited.

[0172]

Chemical Formula 15

[0173]

[0174]

Chemical Formula 16

[0175]

[0176]

Chemical Formula 17

[0177]

[0178]

Chemical Formula 18

[0179]

[0180]

Chemical Formula 19

[0181]

[0182]

Chemical Formula 20

[0183]

[0184]

Chemical Formula 21

[0185]

[0186]

Chemical Formula 22

[0187]

[0188]

Chemical Formula 23

[0189]

[0190]

Chemical Formula 24

[0191]

[0192]

Chemical Formula 25

[0193]

[0194] As a method for manufacturing the compounds of the present invention, any manufacturing method can be used as long as it can manufacture the compounds.

[0195] As a method for manufacturing the aromatic compounds of the present invention, for example, X in formula (7-1) 8 , X 9 is a sulfur atom; Y 5 , Y 6 is CH; R 38 , R41 is a group represented by formula (2); R 39 , R 40 , R 42 , R 43 is a hydrogen atom; l and n in formula (2) are each 0; Z 1 and Z 2 The aromatic compound (7-1a) having a hydrogen atom can be produced by a method including the following steps A1 to C1.

[0196] (Step A1): A method of preparing a dibromodithiophene biphenylene derivative (Compound 2) with butyl lithium to form a dilithium salt, and synthesizing a dibromodithiophene biphenylene derivative (Compound 3) with a brominating agent.

[0197] (Step B1): A method for producing alkylmagnesium bromide by reacting an alkyl bromide derivative with magnesium.

[0198] (Step C1): A method for producing an aromatic compound (7-1a) by reacting an alkyl zinc chloride derived from an alkyl magnesium bromide obtained in Step B1 with a dibromodithienyl biphenyl olefin derivative (Compound 3) synthesized in Step A1 in the presence of a palladium catalyst.

[0199] The details of each step are as follows.

[0200] (Step A1)

[0201] The step A1 is a method for preparing a dibromo product by converting a dithienyl biphenylene derivative into a dilithium salt with 2 equivalents or more of butyl lithium and reacting the salt with a brominating agent.

[0202] The conditions for preparing the dilithium salt include, for example, using 2 to 3 equivalents of n-butyllithium or tert-butyllithium in a solvent such as THF or diethyl ether at a temperature ranging from -80°C to 20°C.

[0203] As the brominating agent, tetrabromomethane, 1,2-dibromotetrachloroethane, N-bromosuccinimide (hereinafter referred to as "NBS"), etc. can be used.

[0204] (Step B1)

[0205] This step B1 is a method for producing alkylmagnesium bromide by reacting an alkyl bromide derivative with magnesium.

[0206] The conditions for preparing the magnesium salt include, for example, using 1 to 2 equivalents of magnesium in a solvent such as THF or diethyl ether at a temperature ranging from 25°C to 60°C.

[0207] Examples of the alkyl bromide derivative in step B1 include benzyl bromide, 2-phenylethyl bromide, 3-phenylpropyl bromide, 4-phenylbutyl bromide, 4-methylphenethyl bromide, 1-(2-bromoethyl)-4-ethylbenzene, 1-(2-bromoethyl)-4-propylbenzene, 1-(2-bromoethyl)-4-butylbenzene, 1-(2-bromoethyl)-4-pentylbenzene, 1-(2-bromoethyl)-4-hexylbenzene, 1-(2-bromoethyl)-4-heptylbenzene, 1-(2-bromoethyl)-4-octylbenzene, and 5-(2-bromoethyl)-2,3-dihydrobenzofuran.

[0208] (Step C1)

[0209] The step C1 is a method for producing an aromatic compound (7-1a) by reacting an alkylzinc chloride derived from the alkylmagnesium bromide obtained in the step B1 with the dibromodithienylbiphenylene derivative (Compound 3) synthesized in the step A1 in the presence of a palladium catalyst.

[0210] As a method for preparing alkyl zinc chloride, zinc chloride can be used in a solvent such as THF or diethyl ether at a temperature ranging from 0°C to 25°C.

[0211] Examples of the palladium catalyst in step C1 include [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II), tetrakis(triphenylphosphine)palladium, and dichlorobis(triphenylphosphine)palladium. The reaction temperature is in the range of 20°C to 60°C.

[0212] Furthermore, from the viewpoint of reducing the number of reaction steps, a more specific preferred production method is as shown in the following reaction scheme.

[0213]

Chemistry 26

[0214]

[0215] (Here, A and m have the same meanings as A and m shown in formula (2).)

[0216] In addition, X in formula (7-2) 8 , X 9 is a sulfur atom; Y 5 , Y 6 CH; R 38 , R 41 is a group represented by formula (2); R 39 , R 40 , R 42 , R 43 is a hydrogen atom; l and n in formula (2) are each 0; Z 1 and Z 2The aromatic compound (7-2a) having a hydrogen atom can be produced by a method including the following steps D1 to G1.

[0217] (Step D1): A step of producing 1,5-bis(trimethylsilylethynyl)-2,6-difluorobiphenylene by Sonogashira coupling of 1,5-difluoro-2,6-diiodohalobiphenylene with trimethylsilylacetylene in the presence of a palladium / copper catalyst.

[0218] (Step E1): A step of subjecting the 1,5-bis(trimethylsilylethynyl)-2,6-difluorobiphenylene obtained in Step D1 and sodium sulfide to a reaction to produce biphenylene[2,1-b:6,5-b′]dithiophene.

[0219] (Step F1): A step of converting the biphenylene [2,1-b:6,5-b'] dithiophene obtained in Step E1 into a dilithium salt using butyl lithium, and then preparing 2,7-dibromobiphenylene [2,1-b:6,5-b'] dithiophene using a brominating agent.

[0220] (Step G1): A step of reacting an alkylzinc chloride derived from the alkylmagnesium bromide obtained in the aforementioned step B1 with the 2,7-dibromobiphenyl[2,1-b:6,5-b']dithiophene synthesized in step F1 in the presence of a palladium catalyst to produce an aromatic compound (7-2a).

[0221] The details of each step are as follows.

[0222] (Step D1)

[0223] The step D1 is a step of producing 1,5-bis(trimethylsilylethynyl)-2,6-difluorobiphenylene by Sonogashira coupling of 2,6-difluoro-1,5-diiodohalobiphenylene and trimethylsilylacetylene in the presence of a palladium catalyst and a copper catalyst.

[0224] As palladium catalysts at this time, for example, tetrakis(triphenylphosphine)palladium, dichlorobis(triphenylphosphine)palladium, etc. can be mentioned; as copper catalysts, cuprous (I) iodide, cuprous (I) bromide, cuprous (I) chloride, etc. can be mentioned. In addition, in the Sonogashira coupling, it can be carried out in a solvent such as triethylamine, diisopropylamine, diisopropylethylamine, piperidine, pyridine, etc., at a temperature range of 20°C to 80°C. It should be noted that toluene, THF, etc. can be added as a solvent.

[0225] (Step E1)

[0226] The step E1 is a step of producing biphenylene [2,1-b:6,5-b'] dithiophene by reacting the 1,5-bis (trimethylsilylethynyl) -2,6-difluorobiphenylene obtained in the step D1 with sodium sulfide.

[0227] The reaction can be carried out in a solvent such as dimethyl sulfoxide (hereinafter abbreviated as DMSO), N,N-dimethylformamide (hereinafter abbreviated as DMF), N-methylpyrrolidone (hereinafter abbreviated as NMP) at a temperature ranging from 20 to 200°C.

[0228] This step can also be carried out using known reaction conditions for synthesizing a benzothiophene ring from 2-haloalkynylbenzene (eg Organic Letters, 2009, Vol. 11, pp. 2473-2475).

[0229] (F1 step)

[0230] The step F1 is a method for preparing a dibrominated product by converting the diphenyleno[2,1-b:6,5-b′]dithiophene obtained in the step E1 into a dilithium salt with 2 equivalents or more of butyl lithium and reacting the salt with a brominating agent.

[0231] The conditions for preparing the dilithium salt include, for example, using 2 to 3 equivalents of n-butyllithium or tert-butyllithium in a solvent such as THF or diethyl ether at a temperature ranging from -80°C to 20°C.

[0232] As the brominating agent, tetrabromomethane, 1,2-dibromotetrachloroethane, NBS or the like can be used.

[0233] (G1 step)

[0234] Step G1 is a method for producing an aromatic compound (7-2a) by reacting an alkylzinc chloride derived from the alkylmagnesium bromide obtained in Step B1 with 2,7-dibromobiphenyleno[2,1-b:6,5-b′]dithiophene synthesized in Step F1 in the presence of a palladium catalyst.

[0235] As a method for preparing alkyl zinc chloride, zinc chloride can be used in a solvent such as THF or diethyl ether at a temperature ranging from 0°C to 25°C.

[0236] Examples of the palladium catalyst in step G1 include [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II), tetrakis(triphenylphosphine)palladium, and dichlorobis(triphenylphosphine)palladium. The reaction temperature is in the range of 20°C to 60°C.

[0237] Furthermore, from the viewpoint of reducing the number of reaction steps, a more specific preferred production method is as shown in the following reaction scheme.

[0238]

Chemistry 27

[0239]

[0240] (Here, A and m have the same meanings as A and m shown in formula (2))

[0241] X in formula (7-5) 8 , X 9 is a sulfur atom; Y 5 , Y 6 CH; R 38 , R 41 is a group represented by formula (2); R 39 , R 40 , R 42 , R 43 , R 71 , R 72 is a hydrogen atom; l and n in formula (2) are each 0; Z 1 and Z 2 The aromatic compound (7-5a) having a hydrogen atom can be produced by a method comprising the steps of the following A2, the above-mentioned B1, and the following C2.

[0242] (Step A2): A method of preparing a dibromodithiophene anthracene derivative (Compound 19) with butyl lithium to form a dilithium salt, and synthesizing a dibromodithiophene anthracene derivative (Compound 20) with a brominating agent.

[0243] (Step C2): A method for preparing an aromatic compound (7-5a) by reacting an alkylzinc bromide derived from an alkylmagnesium bromide obtained in Step B1 with a dibromobisthiopheneanthracene derivative (Compound 20) synthesized in Step A2 in the presence of a palladium catalyst.

[0244] The details of each step are as follows.

[0245] (Step A2)

[0246] The step A2 is a method for preparing a dibrominated product by converting a bithiopheneanthracene derivative into a dilithium salt using 2 or more equivalents of butyl lithium and reacting the salt with a brominating agent.

[0247] The conditions for preparing the dilithium salt include, for example, using 2 to 3 equivalents of n-butyllithium or tert-butyllithium in a solvent such as THF or diethyl ether at a temperature ranging from -80°C to 20°C.

[0248] As the brominating agent, tetrabromomethane, 1,2-dibromotetrachloroethane, or the like can be used.

[0249] (C2 step)

[0250] The step C2 is a method for producing an aromatic compound (7-5a) by reacting an alkylzinc chloride derived from the alkylmagnesium bromide obtained in the step B1 with the dibromobithiopheneanthracene derivative (Compound 20) synthesized in the step A2 in the presence of a palladium catalyst.

[0251] As a method for preparing alkylzinc bromide, zinc chloride can be used in a solvent such as THF or diethyl ether at a temperature ranging from 0°C to 25°C.

[0252] Examples of the palladium catalyst in step C2 include [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II), tetrakis(triphenylphosphine)palladium, and dichlorobis(triphenylphosphine)palladium. Examples of the reaction temperature include 20°C to 60°C.

[0253] Furthermore, from the viewpoint of reducing the number of reaction steps, a more specific preferred production method is as shown in the following reaction scheme.

[0254]

Chemistry 28

[0255]

[0256] (Here, A and m have the same meanings as A and m shown in formula (2))

[0257] X in formula (7-1) 8 , X 9 is a sulfur atom; Y 5 , Y 6 CH; R 38 is a group represented by formula (2); R 39 ~R 43 is a hydrogen atom; l and n in formula (2) are each 0; Z 1 and Z 2 The aromatic compound (7-1b) having a hydrogen atom can be produced by a method comprising the following steps A3, B1, and C3.

[0258] (Step A3): A method of preparing a monobromodithiophene biphenylene derivative (Compound 2) by using butyl lithium to prepare a monolithium salt, and then synthesizing a monobromodithiophene biphenylene derivative (Compound 21) by using a brominating agent.

[0259] (Step C3): A method for preparing an aromatic compound (7-1b) by reacting an alkylzinc bromide derived from an alkylmagnesium bromide obtained in Step B1 with a monobromodithienylbiphenylene derivative (Compound 21) synthesized in Step A3 in the presence of a palladium catalyst.

[0260] The details of each step are as follows.

[0261] (Step A3)

[0262] The A3 step is a method of preparing a monolithium salt from a dithiophene biphenylene derivative using 1.0 equivalent of butyllithium and reacting it with a brominating agent to produce a monobromide therefrom.

[0263] As the conditions for preparing the monolithium salt, for example, 0.5 to 1.5 equivalents of n-butyllithium or tert-butyllithium can be used, and the reaction can be carried out in a solvent such as THF or diethyl ether within a temperature range of -80°C to 20°C.

[0264] As the brominating agent, carbon tetrabromide, 1,2-dibromotetrachloroethane, etc. can be used.

[0265] (Step C3)

[0266] The C3 step is a method of producing an aromatic compound (7-1b) by reacting an alkylzinc chloride derived from an alkylmagnesium bromide obtained through the B1 step with a monobromodithiophene biphenylene derivative (Compound 21) synthesized in the A3 step in the presence of a palladium catalyst.

[0267] As a method for preparing alkylzinc bromide, zinc chloride can be used, and the reaction can be carried out in a solvent such as THF or diethyl ether within a temperature range of 0°C to 25°C.

[0268] Examples of the palladium catalyst in the C3 step include dichlorobis(η5-cyclopentadienyl) palladium(II), tetrakis(triphenylphosphine)palladium, dichlorobis(triphenylphosphine)palladium, etc.; examples of the reaction temperature include a range of 20°C to 60°C.

[0269] Furthermore, from the viewpoint of having fewer reaction steps, a more preferred specific production method is as shown in the following reaction route.

[0270] [Chemical Formula 29]

[0271]

[0272] (Here, A and m have the same meanings as A and m shown in Formula (2))

[0273] X in Formula (7-5) 8 , X 9 is a sulfur atom; Y 5 , Y 6 is CH; R 38 is the group shown in Formula (2); R 39 to R 41 , R 42 , R 43 , R 71 , R 72 is a hydrogen atom; l and n in Formula (2) are each 0; Z 1and Z 2 The aromatic compound (7-5b) which is a hydrogen atom can be produced by isolating it as a by-product of the above step C2, or by a method involving the following step A4, the above step B1, and the following step C4.

[0274] (Step A4): A method of preparing a monobromobisthiophene anthracene derivative (Compound 19) with butyl lithium to form a monolithium salt, and synthesizing a monobromobisthiophene anthracene derivative (Compound 22) with a brominating agent.

[0275] (Step C4): A method for preparing an aromatic compound (7-5b) by reacting an alkylzinc bromide derived from the alkylmagnesium bromide obtained in Step B1 with the monobromobisthiopheneanthracene derivative (Compound 22) synthesized in Step A4 in the presence of a palladium catalyst.

[0276] The details of each step are as follows.

[0277] (Step A4)

[0278] The step A4 is a method for preparing a monobrominated product by converting a bithiophene anthracene derivative into a monolithium salt using 1 equivalent of butyl lithium and reacting the salt with a brominating agent.

[0279] The monolithium salt can be prepared, for example, using 0.5 to 1.5 equivalents of n-butyl lithium or tert-butyl lithium in a solvent such as THF or diethyl ether at a temperature ranging from -80°C to 20°C.

[0280] As the brominating agent, tetrabromomethane, 1,2-dibromotetrachloroethane, or the like can be used.

[0281] (C4 step)

[0282] The step C4 is a method for producing an aromatic compound (7-5b) by reacting an alkylzinc chloride derived from the alkylmagnesium bromide obtained in the step B1 with the monobromobisthiopheneanthracene derivative (Compound 22) synthesized in the step A4 in the presence of a palladium catalyst.

[0283] As a method for preparing alkylzinc bromide, zinc chloride can be used in a solvent such as THF or diethyl ether at a temperature ranging from 0°C to 25°C.

[0284] Examples of the palladium catalyst in step C4 include [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II), tetrakis(triphenylphosphine)palladium, and dichlorobis(triphenylphosphine)palladium. The reaction temperature is in the range of 20°C to 60°C.

[0285] Furthermore, from the viewpoint of reducing the number of reaction steps, a more specific preferred production method is as shown in the following reaction scheme.

[0286]

Chemistry 30

[0287]

[0288] (Here, A and m have the same meanings as A and m shown in formula (2))

[0289] The compound of the present invention can be dissolved in a suitable solvent to form a solution for forming an organic semiconductor layer containing the compound. As the solvent, any solvent can be used as long as it is a solvent that can dissolve the aromatic compound shown in formula (1-I) or formula (1-II). From the viewpoint of the drying speed of a suitable solvent when forming an organic semiconductor layer, an organic solvent having a boiling point of more than 100° C. at normal pressure is preferably used.

[0290] The solvent that can be used in the present invention is not particularly limited, and examples thereof include aromatic hydrocarbons such as toluene, mesitylene, o-xylene, isopropylbenzene, pentylbenzene, cyclohexylbenzene, 1,2,4-trimethylbenzene, tetralin, and indane; aromatic ethers such as anisole, 2-methylanisole, 3-methylanisole, 2,3-dimethylanisole, 3,4-dimethylanisole, 2,6-dimethylanisole, ethylphenyl ether, butylphenyl ether, 1,2-methylenedioxybenzene, and 1,2-ethylenedioxybenzene; and aromatic halogen compounds such as chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, 1,2-difluorobenzene, 1,3-difluorobenzene, and 1,4-difluorobenzene. Thiophene, 3-chlorothiophene, 2-chlorothiophene, 3-methylthiophene, 2-methylthiophene, benzothiophene, 2-methylbenzothiophene, 2,3-dihydrobenzothiophene, furan, 3-methylfuran, 2-methylfuran, 2,5-dimethylfuran, benzofuran, 2-methylbenzofuran, 2,3-dihydrobenzofuran, thiazole, oxazole, benzothiazole, benzoxazole, pyridine and other heteroaromatics; hexane, cyclohexane, heptane, octane, nonane, decane, undecane, dodecane, decahydronaphthalene and other saturated hydrocarbons; dipropylene glycol dimethyl ether, dipropylene glycol diacetate, dipropylene glycol methyl-n-propyl ether, dipropylene glycol methyl ether acetate, 1,4-butanediol diacetate, 1,3-butanediol diethyl diols such as esters, 1,3-butanediol diacetate, 1,6-hexanediol diacetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate; esters such as dimethyl phthalate, diethyl phthalate, dimethyl terephthalate, phenyl acetate, cyclohexanol acetate, 3-methoxybutyl acetate, tetrahydrofurfuryl acetate, tetrahydrofurfuryl propionate, and γ-butyrolactone; cyclic ethers such as THF and 2-methoxymethyltetrahydrofuran, among which toluene, o-xylene, mesitylene, 1,2,4-trimethylbenzene, tetrahydrofurfuryl propionate, and γ-butyrolactone are preferred from the viewpoint of having a moderate drying speed. Preferably, the phthalene, indane, octane, nonane, decane, anisole, 2-methylanisole, 3-methylanisole, 2,3-dimethylanisole, 3,4-dimethylanisole, 2,6-dimethylanisole, ethylphenyl ether, butylphenyl ether, 1,2-methylenedioxybenzene, 1,2-ethylenedioxybenzene, chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, 3-methylthiophene, benzothiazole, and more preferably, toluene, o-xylene, mesitylene, tetralin, indane, octane, nonane, decane, anisole, 2-methylanisole, 3-methylanisole, 2,3-dimethylanisole, 3,4-dimethylanisole, 2,6-dimethylanisole.

[0291] The solvent used in the present invention may be used alone or as a mixture of two or more solvents having different properties such as boiling point, polarity, solubility parameter, etc.

[0292] The temperature at which the aromatic compound represented by formula (1-I) or (1-II) is mixed and dissolved in a solvent is preferably in the range of 0 to 80°C, more preferably in the range of 10 to 60°C, for the purpose of promoting dissolution.

[0293] The time for dissolving and mixing the aromatic compound represented by formula (1-I) or (1-II) in the organic solvent is preferably 1 minute to 1 hour in order to obtain a uniform solution.

[0294] In the present invention, if the concentration of the aromatic compound represented by formula (1-I) or formula (1-II) in the organic semiconductor layer forming solution of the present invention is in the range of 0.1 to 10.0 wt %, the handling becomes easy and the efficiency of forming the organic semiconductor layer is more excellent. In addition, if the viscosity of the organic semiconductor layer forming solution is in the range of 0.3 to 10 mPa·s, more suitable coating properties are exhibited.

[0295] It should be noted that the aromatic compound itself has moderate agglomeration, so the solution can be prepared at a relatively low temperature, and the solution has oxidation resistance, so it can be suitably applied to the manufacture of an organic film by a coating method. That is, since there is no need to remove air from the atmosphere, the coating step can be simplified. Further, as a binder that can be present in the solution, for example, polystyrene, poly (α-methylstyrene), poly (4-methylstyrene), poly (1-vinylnaphthalene), poly (2-vinylnaphthalene), poly (styrene-block-butadiene-block-styrene), poly (styrene-block-isoprene-block-styrene), poly (vinyltoluene), poly (styrene-co-2,4-dimethylstyrene), poly (chlorostyrene), poly (styrene-co-α-methylstyrene), poly (styrene-co-butadiene), poly (ethylene-co-norbornene) can be cited. ), polyphenylene ether, polycarbonate, polycarbazole, polytriarylamine, poly(9,9-dioctylfluorene-co-dimethyltriarylamine), poly(N-vinylcarbazole), polymethyl methacrylate, poly(styrene-co-methyl methacrylate), polyethyl methacrylate, poly-n-propyl methacrylate, polyisopropyl methacrylate, poly-n-butyl methacrylate, polyphenyl methacrylate, polymethyl acrylate, polyethyl acrylate, poly-n-propyl acrylate, etc., preferably polystyrene, poly(α-methylstyrene), poly(ethylene-co-norbornene), polymethyl methacrylate and other polymers. In order to obtain a moderate solution viscosity, the concentration of these polymer binders is preferably 0.001 to 10.0% by weight.

[0296] From the viewpoint of being more suitable for coping with process temperatures during electronic device production, the glass transition temperature (Tg) of the polymer binder is preferably 105° C. or higher, more preferably 120° C. or higher, and particularly preferably 150° C. or higher.

[0297] In order to obtain an organic thin film transistor with higher carrier mobility, the molecular weight of the polymer is preferably 5000 to 1000000, more preferably 10000 to 500000, and particularly preferably 20000 to 100000. In the present invention, the molecular weight of the polymer refers to the weight average molecular weight (Mw) in terms of polystyrene.

[0298] This polymer has an effect as a general polymer binder and improves the film-forming property of the obtained organic semiconductor layer. An insulating polymer and a semiconducting polymer can also be used.

[0299] Specific examples of the polymer that can be used as the polymer binder in the present invention include, in addition to the polymers listed above, polar cyclic polyolefins, polysulfones, acrylonitrile-styrene copolymers, methyl methacrylate-styrene copolymers, and the like.

[0300] More specifically, the polar cyclic polyolefin is more preferably a polymer represented by the following formula (9).

[0301]

Chemistry 31

[0302]

[0303] (Here, R 62 ~R 64 Each independently represents one selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, a cyano group, a nitro group, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a hydroxyl group, an amino group, or an alkylamino group having 1 to 20 carbon atoms; Z represents one selected from a halogen atom, an alkoxycarbonyl group having 2 to 20 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, a cyano group, a nitro group, an alkoxy group having 1 to 20 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, a hydroxyl group, an amino group, or an alkylamino group having 1 to 20 carbon atoms; p represents an integer of 20 to 5000, and q and r each independently represent an integer of 0 to 2; a bond including a solid line and a dotted line represents a single bond or a double bond.

[0304] R in formula (9) 62 ~R 64Each independently represents one selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, a cyano group, a nitro group, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a hydroxyl group, an amino group, or an alkylamino group having 1 to 20 carbon atoms, and in order to obtain high heat resistance, a hydrogen atom or an alkyl group having 1 to 20 carbon atoms is preferred.

[0305] R 62 ~R 64 The alkyl group having 1 to 20 carbon atoms in the alkyl group may include, for example, a straight-chain or branched alkyl group such as a methyl group, an ethyl group, a n-propyl group, a n-butyl group, an isobutyl group, a sec-butyl group, and a n-pentyl group. The aryl group having 6 to 20 carbon atoms may include, for example, a phenyl group, a p-tolyl group, a p-(n-hexyl)phenyl group, a p-(n-octyl)phenyl group, and a p-(2-ethylhexyl)phenyl group. The alkoxycarbonyl group having 2 to 20 carbon atoms may include, for example, a methoxycarbonyl group, an ethoxycarbonyl group, and a n-propoxycarbonyl group. The aryloxycarbonyl group having 7 to 20 carbon atoms may include, for example, a phenoxycarbonyl group and a 4-methylphenoxycarbonyl group. The alkoxy group having 1 to 20 carbon atoms may include, for example, a methoxy group, an ethoxy group, and a n-propoxy group. The aryloxy group having 6 to 20 carbon atoms may include, for example, a phenoxy group and a 4-methylphenoxy group. The alkylamino group having 1 to 20 carbon atoms may include, for example, a methylamino group, an ethylamino group, and a n-propylamino group. And wherein, in order to obtain high heat resistance, the substituent R 60 Preferably, methyl, ethyl, or n-propyl, the substituent R 63 and R 64 Preferred is a hydrogen atom.

[0306] Z in formula (9) represents one selected from a halogen atom, an alkoxycarbonyl group having 2 to 20 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, a cyano group, a nitro group, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a hydroxyl group, an amino group, or an alkylamino group having 1 to 20 carbon atoms.

[0307] Examples of the alkoxycarbonyl group having 2 to 20 carbon atoms in the substituent Z include methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, n-butoxycarbonyl, n-hexyloxycarbonyl, cyclohexyloxycarbonyl, etc., and examples of the aryloxycarbonyl group having 7 to 20 carbon atoms include phenoxycarbonyl, 4-methylphenoxycarbonyl, 2,4-dimethylphenoxycarbonyl, 4-ethylphenoxycarbonyl, etc. Examples of the alkoxy group having 1 to 20 carbon atoms include methoxy and ethoxy. Examples of the aryloxy group having 6 to 20 carbon atoms include phenoxy and 4-methylphenoxy. Examples of the alkylamino group having 1 to 20 carbon atoms include methylamino, ethylamino, n-propylamino, etc. In order to obtain high solubility and high heat resistance, an alkoxycarbonyl group having 2 to 20 carbon atoms is preferred.

[0308] p represents an integer of 20 to 5000, and is preferably 40 to 2000 in order to obtain an organic thin film transistor with a higher carrier mobility. q represents an integer of 0 to 2, and is preferably 1. r represents an integer of 0 to 2, and is preferably 0 or 1. More preferably, 0.

[0309] The bonds including solid lines and dotted lines represent single bonds or double bonds, and single bonds are preferred for obtaining thermal stability.

[0310] The polysulfones used as the polymer binder in the present invention are not particularly limited as long as they have a polysulfone structure, and more specifically, the polysulfones shown in the following polysulfones 1 to 5 can be cited.

[0311]

Chemistry 32

[0312]

[0313] (Here, the substituent R 65 ~R 68 Each independently represents an alkyl group having 1 to 20 carbon atoms, and s represents an integer of 10 to 20,000.

[0314] Substituent R 65 ~R 68 The alkyl group having 1 to 20 carbon atoms in the alkyl group includes, for example, a straight-chain or branched-chain alkyl group such as a methyl group, an ethyl group, a n-propyl group, a n-butyl group, an isobutyl group, a n-pentyl group, a n-hexyl group, an isohexyl group, a n-heptyl group, a n-octyl group, a n-nonyl group, a n-decyl group, a n-dodecyl group, a n-tetradecyl group, a n-octadecyl group, a 2-ethylhexyl group, a 3-ethylheptyl group, a 3-ethyldecyl group, and a 2-hexyldecyl group.

[0315] s represents an integer of 10 to 20,000, and preferably an integer of 10 to 10,000.

[0316] The acrylonitrile-styrene copolymer used as the polymer binder in the present invention is a copolymer of acrylonitrile and styrene in any ratio. From the viewpoint of improved reliability such as exhibiting good electrical properties and smaller changes in threshold voltage when bias stress is applied, the weight ratio of acrylonitrile to styrene is preferably 10:90 to 50:50, and more preferably 20:80 to 40:60.

[0317] The methyl methacrylate-styrene copolymer used as the polymer binder in the present invention is a copolymer of methyl methacrylate and styrene in any ratio. From the viewpoint of improved reliability such as exhibiting good electrical characteristics and smaller changes in threshold voltage when bias stress is applied, the weight ratio of methyl methacrylate to styrene is preferably 1:99 to 90:10, and more preferably 1:99 to 70:30.

[0318] The polymer used as the polymer binder in the present invention can use a polymer whose surface energy is adjusted by a surface treatment agent. As a surface treatment agent, a silane coupling agent can be used, and as its specific example, 1,1,1,3,3,3-hexamethyldisilazane, phenyltrimethoxysilane, octyltrichlorosilane, β-phenylethyltrichlorosilane, β-phenylethyltrimethoxysilane, etc. can be cited. It should be noted that the polymer used in the present invention can use one polymer alone, or can be used as a mixture of more than two polymers. Further, polymers of different molecular weights can also be mixed and used.

[0319] The coating method for forming an organic semiconductor layer using the organic semiconductor layer-forming solution of the present invention is not particularly limited as long as it is a method that can form an organic semiconductor layer. Examples thereof include simple coating methods such as spin coating, drop casting, dip coating, and cast coating; and printing methods such as dispenser coating, inkjet, slit coating, blade coating, flexographic printing, screen printing, gravure printing, and offset printing. Among them, spin coating, drop casting, and inkjet are preferred from the viewpoint of being able to easily and efficiently form an organic semiconductor layer.

[0320] After the organic semiconductor layer forming solution of the present invention is applied, the solvent is removed by drying, thereby forming an organic semiconductor layer using the organic semiconductor layer forming solution.

[0321] When the solvent is dried and removed from the applied organic semiconductor layer, the drying conditions are not particularly limited, and the solvent can be dried and removed under normal pressure or reduced pressure, for example.

[0322] The temperature for drying and removing the organic solvent from the applied organic semiconductor layer is not particularly limited, but is preferably performed at a temperature in the range of 10 to 150° C. in order to efficiently dry and remove the organic solvent from the applied organic semiconductor layer and form the organic semiconductor layer.

[0323] When the organic solvent is dried and removed from the applied organic semiconductor layer, the crystal growth of the aromatic compound represented by formula (1-I) or formula (1-II) can be controlled by adjusting the vaporization rate of the removed organic solvent.

[0324] The film thickness of the organic semiconductor layer formed from the organic semiconductor layer-forming solution of the present invention is not limited, but is preferably in the range of 1 nm to 1 μm, more preferably in the range of 10 nm to 300 nm, from the viewpoint of obtaining good carrier transport.

[0325] Furthermore, the obtained organic semiconductor layer may be subjected to an annealing treatment at 40 to 180° C. after the organic semiconductor layer is formed.

[0326] The organic semiconductor layer formed from the solution for forming an organic semiconductor layer of the present invention can be used as an organic semiconductor device including the organic semiconductor layer, particularly an organic thin-film transistor including the organic semiconductor layer.

[0327] An organic thin film transistor can be obtained by stacking an organic semiconductor layer with a source electrode and a drain electrode and a gate electrode on a substrate via an insulating layer. By using an organic semiconductor layer formed by the organic semiconductor layer forming solution of the present invention in the organic semiconductor layer, an organic thin film transistor exhibiting excellent semiconductor and electrical properties can be made.

[0328] Figure 1 , a cross-sectional shape of a conventional organic thin film transistor is shown in FIG. Here, (A) is a bottom gate-top contact type, (B) is a bottom gate-bottom contact type, (C) is a top gate-top contact type, and (D) is a top gate-bottom contact type organic thin film transistor, 1 represents an organic semiconductor layer, 2 represents a substrate, 3 represents a gate electrode, 4 represents a gate insulating layer, 5 represents a source electrode, and 6 represents a drain electrode. The organic semiconductor layer formed by the organic semiconductor layer forming solution of the present invention can also be applied to any organic thin film transistor.

[0329] The substrate involved in the present invention is not particularly limited, and examples thereof include plastic substrates such as polyethylene terephthalate, polyethylene naphthalate, polymethyl methacrylate, polymethyl acrylate, polyethylene, polypropylene, polystyrene, cyclic polyolefin, fluorinated cyclic polyolefin, polyimide, polycarbonate, polyvinylphenol, polyvinyl alcohol, poly(diisopropyl fumarate), poly(diethyl fumarate), poly(diisopropyl maleate), polyethersulfone, polyphenylene sulfide, and cellulose triacetate; inorganic material substrates such as glass, quartz, alumina, silicon, heavily doped silicon, silicon oxide, tantalum dioxide, tantalum pentoxide, and indium tin oxide; and metal substrates such as gold, copper, chromium, titanium, and aluminum. It should be noted that when heavily doped silicon is used for the substrate, the substrate can also serve as a gate.

[0330] The gate electrode of the present invention is not particularly limited, and examples thereof include inorganic materials such as aluminum, gold, silver, copper, heavily doped silicon, tin oxide, indium oxide, indium tin oxide, chromium, titanium, tantalum, graphene, carbon nanotubes, etc.; and organic materials such as doped conductive polymers (such as PEDOT-PSS).

[0331] In addition, the above-mentioned inorganic materials can also be used as metal nanoparticle ink without any obstacles. In order to obtain appropriate dispersibility, the solvent at this time is preferably a polar solvent such as water, methanol, ethanol, 2-propanol, 1-butanol, 2-butanol; an aliphatic hydrocarbon solvent with 6 to 14 carbon atoms such as hexane, heptane, octane, decane, dodecane, tetradecane; toluene, xylene, mesitylene, ethylbenzene, pentylbenzene, hexylbenzene, octylbenzene, cyclohexylbenzene, tetralin, indane, anisole, 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, 1,2-dimethylanisole, 2,3-dimethylanisole, 3,4-dimethylanisole, etc. Aromatic hydrocarbon solvents with 7 to 14 carbon atoms. After applying the nanoparticle ink, in order to improve conductivity, it is preferably annealed in a temperature range of 80°C to 200°C.

[0332] The gate insulating layer of the present invention is not particularly limited, and examples thereof include inorganic materials such as silicon oxide, silicon nitride, aluminum oxide, aluminum nitride, titanium oxide, tantalum dioxide, tantalum pentoxide, indium tin oxide, tin oxide, vanadium oxide, barium titanate, bismuth titanate, etc.; polymethyl methacrylate, polymethyl acrylate, polyimide, polyamic acid polycarbonate, polyvinyl phenol, polyvinyl alcohol, poly (diisopropyl fumarate), poly (diethyl fumarate), polyethylene terephthalate, polyethylene diol, polyethylene naphthalate, etc.; Polymer insulating materials such as ethylene formate, polyethyl cinnamate, polymethyl cinnamate, polyethyl crotonate, polyethersulfone, polypropylene-co-1-butene, polyisobutylene, polypropylene, polycyclopentane, polycyclohexane, polycyclohexane-ethylene copolymer, polyfluorocyclopentane, polyfluorocyclohexane, polyfluorocyclohexane-ethylene copolymer, BCB resin (trade name: Cyclotene, manufactured by The Dow Chemical Company), Cytop (trademark), Teflon (trademark), Parylene C, etc., are preferably polymer insulating materials (polymer gate insulating layer) that can be applied by a coating method from the viewpoint of a simple manufacturing method.

[0333] The solvent for dissolving the polymer material is not particularly limited, and examples thereof include aliphatic hydrocarbon solvents having 6 to 14 carbon atoms, such as hexane, heptane, octane, decane, dodecane, and tetradecane; ether solvents such as THF, 1,2-dimethoxyethane, and dioxane; alcohol solvents such as ethanol, isopropanol, 1-butanol, 2-butanol, 2-ethylhexanol, and tetrahydrofurfuryl alcohol; ketone solvents such as acetone, methyl ethyl ketone, diethyl ketone, diisopropyl ketone, and acetophenone; ethyl acetate, γ-butyrolactone, cyclohexyl acetate, 3-methoxybutyl acetate, tetrahydrofurfuryl acetate, and tetrahydrofurfuryl propionate. Ester solvents such as propylene glycol esters; amide solvents such as DMF and NMP; dipropylene glycol dimethyl ether, dipropylene glycol diacetate, dipropylene glycol methyl-n-propyl ether, dipropylene glycol methyl ether acetate, 1,4-butanediol diacetate, 1,3-butanediol diacetate, 1,6-hexanediol diacetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate and other glycol solvents; fluorinated solvents such as perfluorohexane, perfluorooctane, 2-(pentafluoroethyl)hexane, 3-(pentafluoroethyl)heptane, etc.

[0334] The concentration of the polymer insulating material is, for example, 0.1 to 10.0% by weight at a temperature of 20 to 40° C. The thickness of the insulating layer obtained at this concentration is not limited, but is preferably 100 nm to 1 μm, more preferably 150 nm to 900 nm, from the viewpoint of insulation resistance.

[0335] Furthermore, the surfaces of these gate insulating layers may also be modified with silanes such as octadecyltrichlorosilane, decyltrichlorosilane, decyltrimethoxysilane, octyltrichlorosilane, octadecyltrimethoxysilane, β-phenylethyltrichlorosilane, β-phenylethyltrimethoxysilane, phenyltrichlorosilane, phenyltrimethoxysilane, etc.; phosphonic acids such as octadecylphosphonic acid, decylphosphonic acid, octylphosphonic acid; silylamines such as hexamethyldisilazane. Generally, by performing surface treatment on the gate insulating layer, the grain size of the organic semiconductor material can be increased and the molecular orientation can be improved, thereby obtaining the preferred results of improving the carrier mobility, the current switching ratio, and the threshold voltage.

[0336] The material of the source and drain of the organic thin film transistor of the present invention is not particularly limited, and the same material as the gate can be used, the same material as the gate material can be used, or different materials can be stacked. In addition, in order to improve the injection efficiency of carriers, these electrode materials can also be subjected to surface treatment. As the surface treatment agent used in the surface treatment, for example, thiophenol, pentafluorothiophenol, 4-fluorothiophenol, 4-methoxythiophenol, etc. can be cited.

[0337] For fast operation, the carrier mobility of the organic thin film transistor of the present invention is preferably 1.00 cm 2 / V·second or more. In addition, for high switching characteristics, the current switching ratio is preferably 1.0×10 6 above.

[0338] The organic thin film transistor of the present invention can be used for the organic semiconductor layer of transistors such as electronic paper, organic EL displays, liquid crystal displays, IC tags (RFID tags), pressure sensors, biosensors, etc.; organic EL display materials; organic semiconductor laser materials; organic thin film solar cell materials; photonic crystal materials; semiconductor materials for camera elements and other electronic materials. Since the aromatic compound represented by formula (1-I) or formula (1-II) forms a crystalline thin film, it is preferably used as a semiconductor layer of an organic thin film transistor.

[0339] Example

[0340] Hereinafter, the present invention will be described in further detail by way of examples, but the present invention is not limited to these examples.

[0341] Used in product characterization 1 H NMR spectroscopy and liquid chromatography-mass spectrometry (LCMS) analysis.

[0342] < 1 H NMR spectrum analysis>

[0343] Device: Made by JEOL Ltd., (trade name) Delta V5 (400MHz)

[0344] Measurement temperature: 23°C (no temperature specified)

[0345] <Liquid chromatography-mass spectrometry (LCMS) analysis>

[0346] Device: Bruker Daltonics, (trade name) microTOF focus MS Ionization: atmospheric pressure chemical ionization (APCI) method

[0347] LC conditions: the conditions described in the "Liquid Chromatography Analysis" section below

[0348] Thin layer chromatography, gas chromatography (GC), and liquid chromatography (LC) analysis were used to confirm the progress of the reaction, etc. Liquid chromatography analysis was also used to measure the purity of the aromatic compound.

[0349] <Thin layer chromatography analysis>

[0350] Merck PLC silica gel 60F254 0.5 mm was used for thin layer chromatography, and hexane and / or toluene was used as a developing solvent.

[0351] <Gas chromatography analysis>

[0352] Device: Made by Shimadzu Corporation, (trade name) GC2014

[0353] Column: RESTEK Co., Ltd. (trade name) Rxi-1HT, 30 m

[0354] <Liquid chromatography analysis>

[0355] Equipment: Made by Tosoh Corporation (controller: PX-8020, pump: CCPM-II, degassing device: SD-8022)

[0356] Column: Tosoh Co., Ltd., (trade name) ODS-100V, 5 μm, 4.6 mm × 250 mm

[0357] Column temperature: 33°C

[0358] Eluent: dichloromethane: acetonitrile = 2:8 (volume ratio)

[0359] Flow rate: 1.0ml / min

[0360] Detector: UV (manufactured by Tosoh Corporation, (trade name) UV-8020, wavelength: 254 nm).

[0361] The melting point of the aromatic compound was measured using DSC (differential scanning calorimetry).

[0362] <DSC measurement>

[0363] Device: Made by SII Nano Technology Co., Ltd., model: DSC6220

[0364] Heating and cooling speed: 10℃ / min

[0365] Scanning range: -10℃~300℃

[0366] Synthesis Example 1 Synthesis of dibromodithiophene biphenylene derivative (Compound 3) (Step A1)

[0367] Under nitrogen atmosphere, 89.0 mg (0.336 mmol) of a dithiophene biphenylene derivative (compound 2 in the publication) synthesized by the method described in Japanese Patent Application Laid-Open No. 2018-174322 and 9 ml of THF (Fujifilm Wako Pure Chemical Industries, Ltd., dehydrated grade) were added to a 100 ml Schlenk reaction vessel. The mixture was cooled to -80°C, 0.75 mL (1.20 mmol) of 1.6 M n-butyl lithium (Tokyo Chemical Industry Co., Ltd.) was added, stirred for 5 minutes, and then stirred at room temperature for 25 minutes. The mixture was cooled to -78°C, 5 mL of a THF solution of 436 mg (1.34 mmol) of 1,2-dibromotetrachloroethane (Fujifilm Wako Pure Chemical Industries, Ltd., dehydrated grade) was added, and the mixture was stirred while warming to room temperature. Water was added, the solid was filtered, and washed with water, methanol, and hexane to obtain 122 mg (yield 87%) of a yellow solid of a dibromodithiophene biphenylene derivative.

[0368] MS (APCI + )m / z:423(M + +H).

[0369] 1 H NMR (CDCl3, 58° C.): δ = 7.07 (d, J = 7.4 Hz, 2H), 7.05 (s, 2H), δ = 6.65 (d, J = 7.4 Hz, 2H).

[0370] Synthesis Example 2 Synthesis of 2-phenylethylmagnesium bromide (Step B1)

[0371] In a nitrogen atmosphere, 738 mg (30.4 mmol) of magnesium (Fujifilm Wako Pure Chemical Industries, Ltd., crumbs) was added to a 100 mL two-necked flask, and the mixture was stirred for 3 hours under vacuum. In a nitrogen atmosphere, 50 mL of a THF (Fujifilm Wako Pure Chemical Industries, Ltd., dehydrated grade) solution of 3.70 g (20.0 mmol) of (2-bromoethyl)benzene (Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was stirred at room temperature for 1 hour, and then at 45°C for 1.5 hours. The solid was removed by filtration, thereby obtaining a 0.4 M 2-phenylethylmagnesium bromide / THF solution.

[0372] Example 1 Synthesis of 2,7-bis(2-phenylethyl)dithiophene biphenylene (Compound 1) (Step C1)

[0373] In a nitrogen atmosphere, 136 mg (0.997 mmol) of zinc chloride (Fujifilm Wako Pure Chemical Industries, Ltd.) and 3 mL of THF (Fujifilm Wako Pure Chemical Industries, Ltd., dehydrated grade) were added to a 50 mL Schlenk tube, and stirred under ice cooling. Under ice cooling, 1.90 mL (0.760 mmol) of a 0.4 M 2-phenylethylmagnesium bromide / THF solution synthesized in Synthesis Example 2 was added, and stirred at room temperature for 14 hours to prepare a zinc reagent solution.

[0374] On the other hand, 41.2 mg (0.0976 mmol) of the dibromodithiophene-biphenylene derivative synthesized in Synthesis Example 1, 5.20 mg (0.00711 mmol) of [1,1'-bis(diphenylphosphino)ferrocene] dichloropalladium(II) (Sigma-Aldrich), and 4 mL of THF (FUJIFILM Wako Pure Chemical Industries, dehydration grade) were added to a 100 mL Schlenk tube. The previously prepared zinc reagent solution was added dropwise thereto using a Teflon (registered trademark) cannula, and the mixture was stirred at room temperature for 5 hours and then at 55 °C for 1.5 hours. The reaction mixture was cooled in ice, 1 M hydrochloric acid was added, and then toluene was added to separate the phases. The organic phase was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane:toluene = 1 / 0 to 5 / 1 as the solvent). The resulting solid was washed with methanol and recrystallized from hexane / toluene = 12 / 7 to obtain 16.0 mg (yield 35%) of a yellow solid of the aromatic compound (Compound 1).

[0375] MS(APCI + ) m / z: 473 (M + + H).

[0376] 1 1H NMR (CDCl3): δ = 7.32 - 7.22 (m, 10H), 7.00 (d, J = 7.4 Hz, 2H), 6.69 (s, 2H), δ = 6.64 (d, J = 7.4 Hz, 2H), δ = 3.11 (t, J = 7.4 Hz, 4H), δ = 3.03 (t, J = 7.4 Hz, 4H).

[0377] Melting point: 195 °C

[0378] (Compound 1)

[0379]

Chemical Formula 33

[0380]

[0381] Synthesis Example 3 1,4-Dibromo-2,5-bis(trimethylsilylethynyl)benzene

[0382] In a 100 ml Schlenk reaction vessel under a nitrogen atmosphere, 2.62 g (5.36 mmol) of 1,4-dibromo-2,5-diiodobenzene (Tokyo Chemical Industry), 55.8 mg (0.0794 mmol) of bis(triphenylphosphine)palladium dichloride (Fujifilm Wako Pure Chemical Industries, Ltd.), 20.9 mg (0.110 mmol) of copper (I) iodide (Fujifilm Wako Pure Chemical Industries, Ltd.), 10 ml of toluene (Fujifilm Wako Pure Chemical Industries, Ltd., dehydrated grade), and 5 ml of triethylamine (Fujifilm Wako Pure Chemical Industries, Ltd.) were added. 1.67 g (17.0 mmol) of trimethylsilyl acetylene (Fujifilm Wako Pure Chemical Industries, Ltd.) was added to the mixture, and the mixture was stirred at room temperature (25°C) for 50 hours. The resulting reaction mixture was ice-cooled, and 1 M hydrochloric acid was added to quench the reaction. The organic phase was extracted with toluene, washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (solvent: hexane) to obtain 1.14 g (yield 50%) of a solid of the target product.

[0383] 1 H NMR (CDCl3): δ=7.67 (s, 2H), 0.27 (s, 18H).

[0384] Synthesis Example 4 1,4-bis(5-octylthiophene-2-yl)-2,5-bis(trimethylsilylethynyl)benzene

[0385] In a 50 ml Schlenk reaction vessel under a nitrogen atmosphere, 833 mg (3.02 mmol) of 2-bromo-5-octylthiophene (Tokyo Chemical Industry) and 6 ml of THF (Fujifilm Wako Pure Chemical Industries, dehydrated grade) were added. The solution was ice-cooled, and 1.6 ml (3.2 mmol) of a THF solution of ethylmagnesium chloride (Sigma-Aldrich, 2.0 M) was added dropwise. The mixture was aged at 0°C for 220 minutes to prepare a 5-octylthiophene-2-ylmagnesium chloride solution.

[0386] On the other hand, in a nitrogen atmosphere, 527 mg (3.86 mmol) of zinc chloride (Fujifilm Wako Pure Chemical Industries, Ltd.) and 7 ml of THF (dehydration grade) were added to a 100 ml Schlenk reaction vessel, and the mixture was cooled to 0° C. The previously prepared 5-octylthiophene-2-ylmagnesium chloride solution was added dropwise using a Teflon (registered trademark) cannula to the white microslurry solution obtained in this way, and the 100 ml Schlenk reaction vessel and the Teflon (registered trademark) cannula were further washed with 2 ml of THF (dehydration grade) and then added. The obtained mixture was stirred while slowly warming to room temperature. To the generated slurry of 5-octylthiophene-2-ylzinc chloride, 400 mg (0.933 mmol) of 1,4-dibromo-2,5-bis(trimethylsilylethynyl)benzene synthesized in Synthesis Example 3 and 24.0 mg (0.0207 mmol, 2.2 mol% relative to 1,4-dibromo-2,5-bis(trimethylsilylethynyl)benzene) of tetrakis(triphenylphosphine)palladium (Tokyo Chemical Industry) as a catalyst were added. After the reaction was carried out at 60°C for 11 hours, the container was cooled with water and 1M hydrochloric acid was added to stop the reaction. Toluene was added to separate the organic phase, and the organic phase was washed with water and dried over anhydrous sodium sulfate. The mixture was concentrated under reduced pressure, and the obtained residue was purified by silica gel column chromatography (hexane:toluene as a solvent = 1 / 0 to 20 / 1). 541 mg (yield 87%) of 1,4-bis(5-octylthiophene-2-yl)-2,5-bis(trimethylsilylethynyl)benzene was obtained as a yellow solid.

[0387] 1 H NMR (CDCl3): δ=7.68(s,2H), 7.52(d,J=3.7Hz,2H), 6.74(d,J=3.7Hz,2H), 2.83(t,J =7.8Hz,4H), 1.71(m,4H), 1.43~1.28(m,20H), 0.90(t,J=7.3Hz,6H), 0.27(s.18H).

[0388] Synthesis Example 5 1,4-bis(5-octylthiophene-2-yl)-2,5-diethynylbenzene

[0389] Under nitrogen atmosphere, 540 mg (0.819 mmol) of 1,4-bis(5-octylthiophene-2-yl)-2,5-bis(trimethylsilylethynyl)benzene synthesized in Synthesis Example 4, 7 ml of THF, 3.5 ml of methanol and 45.8 mg (0.331 mmol) of potassium carbonate were added to a 100 ml Schlenk reaction vessel. The mixture was stirred at room temperature for 3 hours. The resulting reaction mixture was ice-cooled and 1 M hydrochloric acid was added to stop the reaction. Toluene was added to separate the organic phase, and the organic phase was washed twice with water and dried over anhydrous sodium sulfate. Concentrated under reduced pressure to obtain 422 mg (quant.) of a yellow solid of 1,4-bis(5-octylthiophene-2-yl)-2,5-diethynylbenzene.

[0390] 1 H NMR (CDCl3): δ=7.71(s,2H), 7.50(d,J=3.6Hz,2H), 6.76(d,J=3.5Hz,2H), 3.37(s, 2H), 2.83(t,J=7.8Hz,4H), 1.71(m,4H), 1.43~1.22(m,20H), 0.89(t,J=7.0Hz,6H).

[0391] Synthesis Example 6 2,8-Dioctylanthraquinone[1,2-b:5,6-b']dithiophene

[0392] In a 50 ml Schlenk reaction vessel under a nitrogen atmosphere, 190 mg (0.370 mmol) of 1,4-bis(5-octylthiophene-2-yl)-2,5-diethynylbenzene synthesized in Synthesis Example 5, 6 ml of N,N-dimethylformamide and 20.4 mg of platinum chloride (Fujifilm Wako Pure Chemical Industries, Ltd.) were added. The resulting mixture was stirred at 80°C for 4 hours, and the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (hexane: toluene as a solvent = 10 / 1). Furthermore, recrystallization was performed twice from hexane / toluene = 4 / 1 to obtain 82 mg (yield 43%) of an orange-yellow (Japanese: reddish yellow) solid of 2,8-dioctylanthraquinone[1,2-b:5,6-b']dithiophene.

[0393] 1 H NMR (CDCl3): δ=8.58(s,2H), 7.83(d,J=8.7Hz,2H), 6.69(d,J=8.7Hz,2H), 7.14(s, 2H), 3.00(t,J=7.6Hz,4H), 1.81(m,4H), 1.45~1.22(m,20H), 0.90(t,J=7.0Hz,6H).

[0394] Melting point: 124℃

[0395] (2,8-Dioctylanthra[1,2-b:5,6-b']dithiophene)

[0396]

Chemical 34

[0397]

[0398] Example 2 (Preparation of Solution for Forming Organic Semiconductor Layer)

[0399] In air, 0.87 mg of 2,7-bis(2-phenylethyl)dithienylbiphenylene (Compound 1) synthesized in Example 1 and 434 mg of toluene (FUJIFILM Wako Pure Chemical Industries, Ltd., pure grade) were added to a 10 ml sample tube. After heating to 50 °C and dissolving, it was allowed to cool at room temperature (25 °C) to prepare a solution for forming an organic semiconductor layer. After 10 hours at 25 °C, the solution state was still maintained (the concentration of Compound 1 was 0.20 wt%), and it was confirmed to be a compound suitable for film formation by drop casting and inkjet printing.

[0400] Example 3 (Fabrication of Organic Semiconductor Layer and Organic Thin-Film Transistor)

[0401] Using the solution for forming an organic semiconductor layer obtained in Example 2, a top-gate-bottom-contact type p-type organic thin-film transistor was fabricated. The materials and film formation methods of each component are shown in Table 1.

[0402]

Table 1

[0403]

[0404]

[0405] As a result of evaluating the transfer characteristics of this transistor element, the hole carrier mobility was 1.45 cm 2 / V·s, and the current on-off ratio was 1.6×10 6 .

[0406] Furthermore, the organic thin-film transistor was annealed at 130 °C for 10 minutes, and then its electrical characteristics were measured. The hole carrier mobility was 1.40 cm 2 / V·s, and the current on-off ratio was 1.2×10 6 , and almost no performance degradation was found due to the heat treatment.

[0407] Example 4 (Fabrication of Organic Semiconductor Layer and Organic Thin-Film Transistor)

[0408] Using the solution for forming an organic semiconductor layer obtained in Example 2 and using the materials and film formation methods of various components shown in Example 3, a bottom-gate-bottom-contact type p-type organic thin-film transistor was fabricated.

[0409] The transfer characteristics of the transistor element were evaluated and the carrier mobility of holes was 2.29 cm 2 / V·second, the current switching ratio is 1.5×10 6 .

[0410] Furthermore, the organic thin film transistor was annealed at 130°C for 10 minutes, and then its electrical characteristics were measured. The carrier mobility of holes was 2.25 cm 2 / V·second, the current switching ratio is 1.0×10 6 , almost no performance degradation due to heat treatment was found.

[0411] Synthesis Example 7 Synthesis of 4-propylphenylethanol

[0412] In a 100 ml Schlenk reaction vessel under a nitrogen atmosphere, 5.03 g (25.3 mmol) of 1-bromo-4-propylbenzene (Tokyo Chemical Industry) and 80 ml of THF (Fujifilm Wako Pure Chemical Industries, dehydrated grade) were added. The mixture was cooled to -78°C, 19.0 mL (30.4 mmol) of 1.6 M n-butyllithium (Tokyo Chemical Industry) was added, and the mixture was stirred at -78°C for 90 minutes. 25.0 ml (30.0 mmol) of a 1.2 M ethylene oxide THF solution (Tokyo Chemical Industry) was added at -78°C, and the mixture was stirred while warming to room temperature. After adding 1 M hydrochloric acid, diethyl ether was added to separate the phases. The organic phase was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (solvent: dichloromethane) to obtain 2.55 g (yield 58%) of a colorless liquid of 4-propylphenethyl alcohol.

[0413] 1 H NMR (CDCl3): δ=7.11(s,4H), 3.85(m,2H), 2.85(t,J=6.5Hz,2H), 2.57(t,J=7.5Hz,2H), 1.69-1.59(m,2H), 1.51-1.47(m,1H), 0.95(t,J=7.3Hz,3H).

[0414] Synthesis Example 8 Synthesis of 1-(2-bromoethyl)-4-propylbenzene

[0415] In a 100 ml two-necked flask under a nitrogen atmosphere, 1.07 g (6.54 mmol) of 4-propylphenylethanol synthesized in Synthesis Example 7 and 30 ml of dichloromethane (Fujifilm Wako Pure Chemical Industries, Ltd., dehydrated grade) were added. The solution was ice-cooled, and 0.60 ml (6.32 mmol) of phosphorus tribromide was added, stirred for 20 minutes, and then stirred at room temperature for 22 hours. The reaction solution was poured into ice, neutralized with a saturated sodium bicarbonate aqueous solution, and then dichloromethane was added to separate the phases. The organic phase was washed with a saturated sodium bicarbonate aqueous solution and water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (solvent: dichloromethane) to obtain 489 mg (yield 33%) of 1-(2-bromoethyl)-4-propylbenzene as a colorless liquid.

[0416] 1 H NMR (CDCl3): δ=7.13(s,4H), 3.56(t,J=7.7Hz,2H), 3.14(t,J=7.7Hz,2H), 2. 57(t,J=7.6Hz,2H), 1.64(dt,J=7.6Hz,J=7.3Hz,2H), 0.95(t,J=7.3Hz,3H).

[0417] Synthesis Example 9 Synthesis of 2-(4-propylphenyl)ethylmagnesium bromide (Step B1)

[0418] In a nitrogen atmosphere, 42.1 mg (1.73 mmol) of magnesium (Fujifilm Wako Pure Chemical Industries, Ltd., crumbs) was added to a 100 mL two-necked flask, and the mixture was stirred for 2 hours under vacuum. In a nitrogen atmosphere, 5 mL of a THF (Fujifilm Wako Pure Chemical Industries, Ltd., dehydrated grade) solution of 231 mg (1.02 mmol) of 1-(2-bromoethyl)-4-propylbenzene synthesized in Synthesis Example 8 was added, and the mixture was stirred at room temperature for 90 minutes and then at 40° C. for 1 hour. The solid was removed by filtration, thereby obtaining a 0.2 M 2-(4-propylphenyl)ethylmagnesium bromide / THF solution.

[0419] Example 5 Synthesis of 2,7-bis(2-(4-propylphenyl)ethyl)dithiophene biphenylene (Compound 4) (Step C1)

[0420] In a nitrogen atmosphere, 169 mg (1.24 mmol) of zinc chloride (Fujifilm Wako Pure Chemical Industries, Ltd.) and 2 mL of THF (Fujifilm Wako Pure Chemical Industries, Ltd., dehydrated grade) were added to a 50 mL Schlenk tube, and stirred under ice cooling. Under ice cooling, 5.00 mL (1.00 mmol) of a 0.2 M 2-(4-propylphenyl)ethylmagnesium bromide / THF solution synthesized in Synthesis Example 9 was added, and stirred under ice cooling for 30 minutes, and then stirred at room temperature for 14 hours to prepare a zinc reagent solution.

[0421] On the other hand, 51.0 mg (0.121 mmol) of the dibromodithiophene biphenylene derivative synthesized in Synthesis Example 1, 8.60 mg (0.0131 mmol) of [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (Sigma-Aldrich), and 6 mL of THF (Fujifilm Wako Pure Chemical Industries, Ltd., dehydrated grade) were added to a 100 mL Schlenk tube. The previously prepared zinc reagent solution was added dropwise using a Teflon (registered trademark) cannula, and stirred at room temperature for 8 hours. The reaction mixture was ice-cooled, 1 M hydrochloric acid was added, and toluene was added to separate the phases. The organic phase was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane as a solvent: toluene = 1 / 0 to 2 / 1). The obtained solid was rinsed with methanol and purified by recrystallization from toluene to obtain 43.6 mg (yield 65%) of 2,7-bis(2-(4-propylphenyl)ethyl)dithienobiphenylene (Compound 4) as a yellow solid.

[0422] 1 H NMR (CDCl3): δ=7.13(m,8H), 6.99(d,J=7.6Hz,2H), 6.69(s,2H), 6.64(d,J=7.6Hz,2H), 3.09(t,J=6.7Hz, 4H), 2.99 (t, J=6.7Hz, 4H), 2.57 (t, J=7.4Hz, 4H), 1.64 (dt, J=7.4Hz, J=7.2Hz, 4H), 0.95 (t, J=7.2Hz, 6H).

[0423] Melting point: 230℃

[0424] (Compound 4)

[0425]

Chemistry 35

[0426]

[0427] Synthesis Example 10 Synthesis of 4-butylphenylethanol

[0428] Under nitrogen atmosphere, 4.34 g (20.4 mmol) of 1-bromo-4-butylbenzene (Tokyo Chemical Industry) and 80 ml of THF (Fujifilm Wako Pure Chemical Industries, dehydrated grade) were added to a 300 ml Schlenk reaction vessel. The mixture was cooled to -78°C, 26.0 mL (41.6 mmol) of 1.6 M n-butyl lithium (Tokyo Chemical Industry) was added, and stirred at -78°C for 2 hours. 25.0 ml (30.0 mmol) of 1.2 M ethylene oxide THF solution (Tokyo Chemical Industry) was added at -78°C, and stirred while warming to room temperature. After adding 1 M hydrochloric acid, diethyl ether was added and the phases were separated. The organic phase was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (as solvent, hexane:dichloromethane=1 / 1 to 0 / 1, ethyl acetate) to obtain 2.20 g (yield 60%) of 4-butylphenethanol as a colorless liquid.

[0429] 1 H NMR (CDCl3): δ=7.14(s,4H), 3.85(m,2H), 2.84(t,J=6.5Hz,2H), 2.59(t,J=7.8Hz,2H), 1.63-1.56(m,2H), 1.41-1.32(m,1H), 0.93(t,J=7.3Hz,3H).

[0430] Synthesis Example 11 Synthesis of 1-(2-bromoethyl)-4-butylbenzene

[0431] In a 100 ml two-necked flask under a nitrogen atmosphere, 2.20 g (12.3 mmol) of 4-butylphenylethanol synthesized in Synthesis Example 10 and 30 ml of dichloromethane (Fujifilm Wako Pure Chemical Industries, Ltd., dehydrated grade) were added. The solution was ice-cooled, and 2.40 ml (25.2 mmol) of phosphorus tribromide was added, stirred for 10 minutes, and then stirred at room temperature for 25 hours. The reaction solution was poured into ice, neutralized with a saturated sodium bicarbonate aqueous solution, and then dichloromethane was added to separate the phases. The organic phase was washed with a saturated sodium bicarbonate aqueous solution and water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (solvent: dichloromethane) to obtain 922 mg (yield 31%) of 1-(2-bromoethyl)-4-butylbenzene as a colorless liquid.

[0432] 1 H NMR (CDCl3): δ=7.13(m,4H), 3.56(t,J=7.7Hz,2H), 3.14(t,J=7.7Hz,2H), 2.59 (t,J=7.7Hz,2H), 1.61-1.57(m,2H), 1.41-1.31(m,2H), 0.93(t,J=7.3Hz,3H).

[0433] Synthesis Example 12 Synthesis of 2-(4-butylphenyl)ethylmagnesium bromide (Step B1)

[0434] In a nitrogen atmosphere, 41.2 mg (1.69 mmol) of magnesium (Fujifilm Wako Pure Chemical Industries, Ltd., crumbs) was added to a 100 mL two-necked flask, and the mixture was stirred for 2 hours under vacuum. In a nitrogen atmosphere, 5 mL of a THF (Fujifilm Wako Pure Chemical Industries, Ltd., dehydrated grade) solution of 248 mg (1.03 mmol) of 1-(2-bromoethyl)-4-butylbenzene synthesized in Synthesis Example 11 was added, and the mixture was stirred at room temperature for 30 minutes and then at 40° C. for 1 hour. The solid was removed by filtration to obtain a 0.2 M 2-(4-butylphenyl)ethylmagnesium bromide / THF solution.

[0435] Example 6 Synthesis of 2,7-bis(2-(4-butylphenyl)ethyl)dithiophene biphenylene (Compound 5) (Step C1)

[0436] In a nitrogen atmosphere, 189 mg (1.39 mmol) of zinc chloride (Fujifilm Wako Pure Chemical Industries, Ltd.) and 4 mL of THF (Fujifilm Wako Pure Chemical Industries, Ltd., dehydrated grade) were added to a 50 mL Schlenk tube, and stirred under ice cooling. Under ice cooling, 5.00 mL (1.00 mmol) of a 0.2 M 2-(4-butylphenyl)ethylmagnesium bromide / THF solution synthesized in Synthesis Example 12 was added, and stirred under ice cooling for 30 minutes, and then stirred at room temperature for 17 hours to prepare a zinc reagent solution.

[0437] On the other hand, 50.6 mg (0.120 mmol) of the dibromodithiophene biphenylene derivative synthesized in Synthesis Example 1, 9.40 mg (0.0128 mmol) of [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (Sigma-Aldrich), and 6 mL of THF (Fujifilm Wako Pure Chemical Industries, Ltd., dehydrated grade) were added to a 100 mL Schlenk tube. The previously prepared zinc reagent solution was added dropwise using a Teflon (registered trademark) cannula, and stirred at room temperature for 4 hours. The reaction mixture was ice-cooled, 1 M hydrochloric acid was added, and toluene was added to separate the phases. The organic phase was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane as a solvent: toluene = 1 / 0 to 2 / 1). The obtained solid was rinsed with methanol and purified by recrystallization from hexane / toluene = 1 / 1 to obtain 37.4 mg (yield 53%) of 2,7-bis(2-(4-butylphenyl)ethyl)dithienobiphenylene (Compound 5) as a yellow solid.

[0438] 11H NMR (CDCl3): δ = 7.12 (m, 8H), 6.99 (d, J = 7.4 Hz, 2H), 6.69 (s, 2H), 6.64 (d, J = 7.4 Hz, 2H), 3.09 (t, J = 6.6 Hz, 4H), 2.99 (t, J = 6.6 Hz, 4H), 2.59 (t, J = 7.7 Hz, 4H), 1.61 - 1.57 (m, 4H), 1.40 - 1.31 (m, 4H), 0.93 (t, J = 7.3 Hz, 6H).

[0439] Melting point: 211 °C

[0440] (Compound 5)

[0441]

Chemical Formula 36

[0442]

[0443] Synthesis Example 13 Synthesis of 4-Heptylphenethyl Alcohol

[0444] Under a nitrogen atmosphere, 5.18 g (20.3 mmol) of 1-bromo-4-heptylbenzene (Tokyo Chemical Industry) and 80 ml of THF (FUJIFILM Wako Pure Chemical Industries, dehydration grade) were added to a 300 ml Schlenk reaction vessel. The mixture was cooled to -78 °C, 26.0 mL (41.6 mmol) of 1.6 M n-butyllithium (Tokyo Chemical Industry) was added, and the mixture was stirred at -78 °C for 4 hours. At -78 °C, 25.0 ml (30.0 mmol) of a THF solution of 1.2 M ethylene oxide (Tokyo Chemical Industry) was added, and the mixture was stirred while warming to room temperature. After adding 1 M hydrochloric acid, diethyl ether was added, and the phases were separated. The organic phase was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (solvents: dichloromethane, ethyl acetate) to obtain 3.30 g (yield 74%) of a colorless liquid of 4-heptylphenethyl alcohol.

[0445] 1 1H NMR (CDCl3): δ = 7.14 (s, 4H), 3.85 (m, 2H), 2.85 (t, J = 6.6 Hz, 2H), 2.58 (t, J = 7.6 Hz, 2H), 1.60 (m, 2H), 1.46 (bs, 1H), 1.30 (m, 8H), 0.89 (t, J = 6.8 Hz, 3H).

[0446] Synthesis Example 14 Synthesis of 1-(2-Bromoethyl)-4-heptylbenzene

[0447] In a 100 ml two-necked flask under a nitrogen atmosphere, 3.15 g (14.3 mmol) of 4-heptylphenylethanol synthesized in Synthesis Example 13 and 30 ml of dichloromethane (Fujifilm Wako Pure Chemical Industries, Ltd., dehydrated grade) were added. The solution was ice-cooled, and 1.40 ml (14.7 mmol) of phosphorus tribromide was added, stirred for 30 minutes, and then stirred at room temperature for 19 hours. The reaction solution was poured into ice, neutralized with a saturated sodium bicarbonate aqueous solution, and then dichloromethane was added to separate the phases. The organic phase was washed with a saturated sodium bicarbonate aqueous solution and water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (solvent: dichloromethane) to obtain 1.74 g (yield 43%) of a colorless liquid of 1-(2-bromoethyl)-4-heptylbenzene.

[0448] 1 H NMR (CDCl3): δ=7.12(m,4H), 3.56(t,J=7.4Hz,2H), 3.13(t,J=7.4Hz,2H), 2.58(t,J=7.6Hz,2H), 1.60(m,2H), 1.30(m,8H), 0.88(t,J=7.0Hz,3H).

[0449] Synthesis Example 15 Synthesis of 2-(4-heptylphenyl)ethylmagnesium bromide (Step B1)

[0450] In a nitrogen atmosphere, 42.1 mg (1.73 mmol) of magnesium (Fujifilm Wako Pure Chemical Industries, Ltd., crumbs) was added to a 100 mL two-necked flask, and the mixture was stirred in a vacuum for 2 hours. In a nitrogen atmosphere, 5 mL of a THF (Fujifilm Wako Pure Chemical Industries, Ltd., dehydrated grade) solution of 288 mg (1.02 mmol) of 1-(2-bromoethyl)-4-heptylbenzene synthesized in Synthesis Example 14 was added, and the mixture was stirred at room temperature for 40 minutes and then at 40° C. for 1 hour. The solid was removed by filtration to obtain a 0.2 M 2-(4-heptylphenyl)ethylmagnesium bromide / THF solution.

[0451] Example 7 Synthesis of 2,7-bis(2-(4-heptylphenyl)ethyl)dithienylbiphenylene (Compound 6) (Step C1)

[0452] In a nitrogen atmosphere, 190 mg (1.40 mmol) of zinc chloride (Fujifilm Wako Pure Chemical Industries, Ltd.) and 4 mL of THF (Fujifilm Wako Pure Chemical Industries, Ltd., dehydrated grade) were added to a 50 mL Schlenk tube, and stirred under ice cooling. Under ice cooling, 5.00 mL (1.00 mmol) of a 0.2 M 2-(4-heptylphenyl)ethylmagnesium bromide / THF solution synthesized in Synthesis Example 15 was added, and stirred under ice cooling for 1 hour, and then stirred at room temperature for 16 hours to prepare a zinc reagent solution.

[0453] On the other hand, 49.8 mg (0.118 mmol) of the dibromodithienylbiphenylene derivative synthesized in Synthesis Example 1, 9.60 mg (0.0131 mmol) of [1,1'-bis(diphenylphosphino)ferrocene] dichloropalladium(II) (Sigma-Aldrich), and 6 mL of THF (FUJIFILM Wako Pure Chemical Industries, dehydration grade) were added to a 50 mL Schlenk tube. A previously prepared zinc reagent solution was added dropwise thereto through a Teflon (registered trademark) cannula, and the mixture was stirred at room temperature for 23 hours. The reaction mixture was cooled in ice, 1 M hydrochloric acid was added, and then toluene was added to separate the phases. The organic phase was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane:toluene = 1 / 0 to 2 / 1 as the solvent). The resulting solid was washed with methanol and recrystallized and purified from hexane / toluene = 1 / 1 to obtain 36.1 mg (yield 46%) of a yellow solid of 2,7-bis(2-(4-heptylphenyl)ethyl)dithienylbiphenylene (Compound 6).

[0454] 1 H NMR (CDCl3): δ = 7.12 (m, 8H), 6.99 (d, J = 7.5 Hz, 2H), 6.69 (s, 2H), 6.64 (d, J = 7.5 Hz, 2H), 3.09 (t, J = 6.8 Hz, 4H), 2.99 (t, J = 6.8 Hz, 4H), 2.58 (t, J = 7.6 Hz, 4H), 1.60 (m, 4H), 1.31 (m, 16H), 0.88 (t, J = 7.1 Hz, 6H).

[0455] Melting point: 198 °C

[0456] (Compound 6)

[0457]

Chemical Formula 37

[0458]

[0459] Synthesis of 2-(2,3-dihydrobenzofuran-5-yl)ethylmagnesium bromide (Synthesis of Step B1) in Synthesis Example 16

[0460] Under a nitrogen atmosphere, 369 mg (15.2 mmol) of magnesium (FUJIFILM Wako Pure Chemical Industries, Ltd., in the form of chips) was added to a 100 mL two-necked flask, and the mixture was stirred under vacuum for 2 hours. Under a nitrogen atmosphere, 25 mL of a THF (FUJIFILM Wako Pure Chemical Industries, Ltd., dehydrated grade) solution of 5-(2-bromoethyl)-2,3-dihydrobenzofuran (Tokyo Chemical Industry Co., Ltd.) 2.27 g (10.0 mmol) was added, and the mixture was stirred at room temperature for 1 hour and then at 40 °C for 1 hour. The solid was removed by filtration to obtain a 0.4 M solution of 2-(2,3-dihydrobenzofuran-5-yl)ethylmagnesium bromide in THF.

[0461] Synthesis of aromatic compound (Compound 7) in Example 8 (Step C1)

[0462] Under a nitrogen atmosphere, 173 mg (1.30 mmol) of zinc chloride (FUJIFILM Wako Pure Chemical Industries, Ltd.) and 5 mL of THF (FUJIFILM Wako Pure Chemical Industries, Ltd., dehydrated grade) were added to a 50 mL Schlenk tube, and the mixture was stirred under ice-cooling. Under ice-cooling, 2.50 mL (1.00 mmol) of the 0.4 M solution of 2-(2,3-dihydrobenzofuran-5-yl)ethylmagnesium bromide in THF synthesized in Synthesis Example 16 was added, and the mixture was stirred under ice-cooling for 30 minutes and then at room temperature for 16 hours to prepare a zinc reagent solution.

[0463] On the other hand, 50.8 mg (0.120 mmol) of the dibromodithiophenylene-biphenylene derivative (Compound 3) synthesized in Synthesis Example 1, 10.4 mg (0.0142 mmol) of [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (Sigma-Aldrich), and 8 mL of THF (FUJIFILM Wako Pure Chemical Industries, Ltd., dehydrated grade) were added to a 50 mL Schlenk tube. The previously prepared zinc reagent solution was added dropwise thereto through a Teflon (registered trademark) cannula, and the mixture was stirred at room temperature for 6 hours. The reaction mixture was cooled under ice-cooling, 1 M hydrochloric acid was added, and then toluene was added to separate the phases. The organic phase was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane:toluene = 1 / 2 to 0 / 1 as the solvent). The resulting solid was washed with methanol and recrystallized from toluene to obtain 4.0 mg (yield 6%) of a yellow solid of the aromatic compound (Compound 7).

[0464] (Compound 7)

[0465]

Chemical Formula 38

[0466]

[0467] Synthesis of 2-(1,2-methylenedioxyphenyl-4-yl)ethanol in Synthesis Example 17

[0468] In a nitrogen atmosphere, 4.03 g (20.1 mmol) of 4-bromo-1,2-methylenedioxybenzene (Tokyo Chemical Industry) and 80 ml of THF (Fujifilm Wako Pure Chemical Industries, dehydrated grade) were added to a 300 ml Schlenk reaction vessel. The mixture was cooled to -78°C, 26.0 mL (41.6 mmol) of 1.6 M n-butyl lithium (Tokyo Chemical Industry) was added, and stirred at -78°C for 4 hours. 25.0 ml (30.0 mmol) of 1.2 M ethylene oxide THF solution (Tokyo Chemical Industry) was added at -78°C, and the mixture was stirred while warming to room temperature. After adding 1 M hydrochloric acid, diethyl ether was added and the phases were separated. The organic phase was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (solvent: dichloromethane, ethyl acetate) to obtain 2.91 g (yield 72%) of 2-(1,2-methylenedioxyphen-4-yl)ethanol as a colorless liquid.

[0469] 1 H NMR (CDCl3): δ=6.76 (d, J=7.8Hz, 1H), 6.72 (s, 1H), 6.68 (d, J=7.8Hz, 1H), 5.94 (s, 2H), 3.82 (m, 2H), 2.79 (t, J=6.4Hz, 2H), 1.43 (m, 1H).

[0470] Synthesis Example 18 Synthesis of 4-(2-bromoethyl)-1,2-methylenedioxybenzene

[0471] Under nitrogen atmosphere, 2.78 g (16.7 mmol) of 2-(1,2-methylenedioxyphenyl-4-yl)ethanol synthesized in Synthesis Example 17 and 20 ml of dichloromethane (Fujifilm Wako Pure Chemical Industries, Ltd., dehydrated grade) were added to a 100 ml two-necked flask. The solution was ice-cooled, 1.60 ml (16.8 mmol) of phosphorus tribromide was added, and after stirring for 30 minutes, it was stirred at room temperature for 20 hours. The reaction solution was poured into ice, neutralized with a saturated aqueous sodium bicarbonate solution, and then dichloromethane was added to separate the phases. The organic phase was washed with a saturated aqueous sodium bicarbonate solution and water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (dichloromethane / hexane as a solvent = 1:5) to obtain 1.03 g (yield 33%) of a colorless liquid of 4-(2-bromoethyl)-1,2-methylenedioxybenzene.

[0472] 1 H NMR (CDCl3): δ=6.76 (d, J=7.9Hz, 1H), 6.69 (s, 1H), 6.66 (d, J=7.9Hz, 1H), 5.95 (s, 2H), 2.52 (t, J=7.6Hz, 2H), 3.08 (t, J=7.6Hz, 2H).

[0473] Synthesis of Synthesis Example 19 Synthesis of 2-(1,2-Methylenedioxyphenyl-4-yl)ethylmagnesium Bromide (Step B1)

[0474] Under a nitrogen atmosphere, 39.1 mg (1.61 mmol) of magnesium (FUJIFILM Wako Pure Chemical Corporation, in the form of chips) was added to a 100 mL two-necked flask, and the mixture was stirred under vacuum for 2 hours. Under a nitrogen atmosphere, 5 mL of a THF (FUJIFILM Wako Pure Chemical Corporation, dehydrated grade) solution of 229 mg (1.00 mmol) of 4-(2-bromoethyl)-1,2-methylenedioxybenzene synthesized in Synthesis Example 18 was added, and the mixture was stirred at room temperature for 40 minutes and then at 40 °C for 1 hour. The solid was removed by filtration to obtain a 0.2 M solution of 2-(1,2-methylenedioxyphenyl-4-yl)ethylmagnesium bromide in THF.

[0475] Synthesis of Aromatic Compound (Compound 8) in Example 9 (Step C1)

[0476] Under a nitrogen atmosphere, 187 mg (1.38 mmol) of zinc chloride (FUJIFILM Wako Pure Chemical Corporation) and 7 mL of THF (FUJIFILM Wako Pure Chemical Corporation, dehydrated grade) were added to a 50 mL Schlenk tube, and the mixture was stirred under ice-cooling. Under ice-cooling, 5.0 mL (1.00 mmol) of the 0.2 M solution of 2-(1,2-methylenedioxyphenyl-4-yl)ethylmagnesium bromide in THF synthesized in Synthesis Example 19 was added, and the mixture was stirred under ice-cooling for 1 hour and then at room temperature for 15 hours to prepare a zinc reagent solution.

[0477] On the other hand, 50.6 mg (0.112 mmol) of the dibromodithiophene-biphenylene derivative (Compound 3) synthesized in Synthesis Example 1, 10.8 mg (0.0148 mmol) of [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (Sigma-Aldrich), and 8 mL of THF (FUJIFILM Wako Pure Chemical Corporation, dehydrated grade) were added to a 50 mL Schlenk tube. The previously prepared zinc reagent solution was added dropwise thereto through a Teflon (registered trademark) cannula, and the mixture was stirred at room temperature for 8 hours. The reaction mixture was cooled with ice, 1 M hydrochloric acid was added, and then toluene was added to separate the phases. The organic phase was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane:toluene = 1 / 2 to 0 / 1 as the solvent). The resulting solid was washed with methanol and recrystallized from toluene to obtain 34.7 mg (yield 55%) of a yellow solid of the aromatic compound (Compound 8).

[0478] (Compound 8)

[0479] [Chemical Formula 39]

[0480]

[0481] Synthesis Example 20 Synthesis of 1,4-bis(thiophen-2-yl)-2,5-bis(trimethylsilylethynyl)benzene

[0482] In a 300 ml Schlenk reaction vessel under a nitrogen atmosphere, 8.18 g (50.2 mmol) of 2-bromo-thiophene (Tokyo Chemical Industry) and 90 ml of THF (Fujifilm Wako Pure Chemical Industries, dehydrated grade) were added. The solution was ice-cooled, and 28.0 ml (56.0 mmol) of a THF solution of ethylmagnesium chloride (Sigma-Aldrich, 2.0 M) was added dropwise. The mixture was aged at 0°C for 3 hours to prepare a thiophene-2-ylmagnesium chloride solution.

[0483] On the other hand, in a nitrogen atmosphere, 9.31 g (68.3 mmol) of zinc chloride (Fujifilm Wako Pure Chemical Industries, Ltd.) and 110 ml of THF (dehydration grade) were added to a 500 ml Schlenk reaction vessel, and the mixture was cooled to 0° C. The previously prepared thiophene-2-ylmagnesium chloride solution was added dropwise to the obtained white fine slurry solution using a Teflon (registered trademark) cannula, and 40 ml of THF (dehydration grade) was added to a 100 ml Schlenk reaction vessel and a Teflon (registered trademark) cannula while washing the same. The obtained mixture was stirred while gradually warming to room temperature. To the generated slurry of thiophen-2-ylzinc chloride, 6.56 g (15.3 mmol) of 1,4-dibromo-2,5-bis(trimethylsilylethynyl)benzene synthesized in Synthesis Example 3 and 515 mg (0.445 mmol, 2.9 mol% relative to 1,4-dibromo-2,5-bis(trimethylsilylethynyl)benzene) of tetrakis(triphenylphosphine)palladium (Tokyo Chemical Industry) as a catalyst were added. After the reaction was carried out at 60°C for 7 hours, the container was cooled with water and 1M hydrochloric acid was added to stop the reaction. Toluene was added to separate the organic phase, and the organic phase was washed with water and dried over anhydrous sodium sulfate. The residue was concentrated under reduced pressure and purified by silica gel column chromatography (hexane:toluene as a solvent = 1 / 10). 5.44 g (yield 82%) of 1,4-bis(thiophen-2-yl)-2,5-bis(trimethylsilylethynyl)benzene as a yellow solid was obtained.

[0484] 1 H NMR (CDCl3): δ=7.74 (s, 2H), 7.70 (dd, J=1.4Hz, J=3.7Hz, 2H), 7.37 (dd, J=1.3Hz, J=5.1Hz, 2H), 7.09 (dd, J=3.7Hz, J=5.1Hz, 2H), 0.26 (s, 18H).

[0485] Synthesis Example 21 Synthesis of 1,4-bis(thiophen-2-yl)-2,5-diethynylbenzene

[0486] Under nitrogen atmosphere, 5.38 g (12.4 mmol) of 1,4-bis(thiophene-2-yl)-2,5-bis(trimethylsilylethynyl)benzene synthesized in Synthesis Example 20, 100 ml of THF, 50 ml of methanol and 801 mg (5.79 mmol) of potassium carbonate were added to a 300 ml eggplant-shaped bottle. The mixture was stirred at room temperature for 6 hours. The resulting reaction mixture was ice-cooled and 1 M hydrochloric acid was added to stop the reaction. Toluene was added to separate the organic phase, and the organic phase was washed twice with water and dried over anhydrous sodium sulfate. Concentrated under reduced pressure to obtain 3.53 g (yield quant.) of a yellow solid of 1,4-bis(thiophene-2-yl)-2,5-diethynylbenzene.

[0487] 1 H NMR (CDCl3): δ=7.78 (s, 2H), 7.67 (dd, J=1.3Hz, J=3.7Hz, 2H), 7.39 (dd, J=1.0Hz, J=5.1Hz, 2H), 7.12 (dd, J=3.7Hz, J=5.1Hz, 2H), 3.37 (s, 2H).

[0488] Synthesis Example 22 Synthesis of anthra[1,2-b:5,6-b']dithiophene (Compound 19)

[0489] In a 200 ml Schlenk reaction vessel under a nitrogen atmosphere, 1.74 g (6.00 mmol) of 1,4-bis(thiophene-2-yl)-2,5-diethynylbenzene synthesized in Synthesis Example 21, 60 ml of N,N-dimethylformamide and 323 mg (1.21 mmol) of platinum chloride (Fujifilm Wako Pure Chemical Industries, Ltd.) were added. The resulting mixture was stirred at 80°C for 4 hours, and the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (hexane:toluene as a solvent = 10 / 1 to 2 / 1) to obtain 701 mg (yield 40%) of a yellow solid of anthra[1,2-b:5,6-b']dithiophene (Compound 19) .

[0490] 1 H NMR (CDCl3): δ=8.73(s,2H), 7.92(d,J=8.9Hz,2H), 7.84(d,J=8.9Hz,2H), 7.56(d,J=5.4Hz,2H), 7.56(d,J=5.4Hz,2H).

[0491] Synthesis Example 23 Synthesis of 2,8-dibromoanthra[1,2-b:5,6-b']dithiophene (Compound 20) (Step A-2)

[0492] In a nitrogen atmosphere, 602 mg (2.07 mmol) of anthra[1,2-b:5,6-b']dithiophene (Compound 19) synthesized in Synthesis Example 22 and 50 ml of THF (Fujifilm Wako Pure Chemical Industries, Ltd., dehydrated grade) were added to a 100 ml Schlenk reaction vessel. The mixture was cooled to -78°C, 6.00 mL (9.60 mmol) of 1.6 M n-butyl lithium (Tokyo Chemical Industry Co., Ltd.) was added, and stirred for 20 minutes, and then stirred at room temperature for 50 minutes. The mixture was cooled to -78°C, and 25 mL of a THF solution of 3.45 g (10.6 mmol) of 1,2-dibromotetrachloroethane (Fujifilm Wako Pure Chemical Industries, Ltd., dehydrated grade) was added, and the mixture was stirred while warming to room temperature. Water was added, and the solid was filtered and washed with water, methanol and hexane to obtain 761 mg (yield 82%) of 2,8-dibromoanthra[1,2-b:5,6-b′]dithiophene (Compound 20) as a yellow solid.

[0493] 1 H NMR (CDCl3, 50° C.): δ = 8.53 (s, 2H), 7.87 (d, J = 8.9 Hz, 2H), 7.87 (d, J = 8.9 Hz, 2H), 7.47 (s, 2H).

[0494] Example 10 Synthesis of 2,8-di(2-phenylethyl)anthraquinone[1,2-b:5,6-b']dithiophene (Compound 10) (Step C2)

[0495] In a nitrogen atmosphere, 413 mg (3.02 mmol) of zinc chloride (Fujifilm Wako Pure Chemical Industries, Ltd.) and 4 mL of THF (Fujifilm Wako Pure Chemical Industries, Ltd., dehydrated grade) were added to a 50 mL Schlenk tube, and stirred under ice cooling. Under ice cooling, 5.60 mL (2.34 mmol) of a 0.4 M 2-phenylethylmagnesium bromide / THF solution synthesized in Synthesis Example 2 was added, and stirred at 0°C for 40 minutes, and then at room temperature for 16 hours to prepare a zinc reagent solution.

[0496] On the other hand, 156 mg (0.348 mmol) of 2,8-dibromoanthraquinone [1,2-b:5,6-b'] dithiophene (Compound 20) synthesized in Synthesis Example 23 and 48.5 mg (0.0662 mmol) of [1,1'-bis (diphenylphosphino) ferrocene] dichloropalladium (II) (Sigma-Aldrich) and 20 mL of THF (Fujifilm Wako Pure Chemical Industries, Ltd., dehydrated grade) were added to a 100 mL Schlenk tube. The previously prepared zinc reagent solution was added dropwise using a Teflon (registered trademark) cannula and stirred at room temperature for 24 hours. The reaction mixture was ice-cooled, 1 M hydrochloric acid was added, and toluene was added to separate the phases. The organic phase was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane as a solvent: toluene = 1 / 0 to 5 / 1). The obtained solid was rinsed with methanol and purified by recrystallization from toluene to obtain 73.2 mg (yield 42%) of 2,8-di(2-phenylethyl)anthraquinone[1,2-b:5,6-b′]dithiophene (Compound 10) as a yellow solid.

[0497] 1 H NMR (CDCl3): δ=8.59(s,2H), 7.85(d,J=8.8Hz,2H), 7.69(d,J=8.8Hz,2H), 7.28(m,10H), 7.14(s,2H), 3.34(t,J=7.6Hz,4H), 3.15(t,J=7.6Hz,4H).

[0498] Melting point: 221°C

[0499] (Compound 10)

[0500]

Chemistry 40

[0501]

[0502] Example 11 Synthesis of 2-(2-phenylethyl)anthraquinone[1,2-b:5,6-b']dithiophene (Compound 15) (Step C2)

[0503] The other component obtained by silica gel column chromatography in Example 10 was purified by recrystallization from hexane to obtain 2.0 mg (yield 1.5%) of 2-(2-phenylethyl)anthraquinone[1,2-b:5,6-b′]dithiophene (Compound 15) as a yellow solid.

[0504] 1H NMR (CDCl3): δ=8.70(s,1H), 8.62(s,1H), 7.90(d,J=8.6Hz,1H), 7.88(d,J=8.4Hz,1H), 7.82(d,J=8.7Hz,1H), 7.71(d,J=8.8 Hz, 1H), 7.54 (d, J = 5.1Hz, 1H), 7.49 (d, J = 5.4Hz, 1H), 7.30 (m, 5H), 7.15 (s, 1H), 3.34 (t, J = 7.7Hz, 4H), 3.16 (t, J = 7.3Hz, 4H).

[0505] Melting point: 174°C

[0506] (Compound 15)

[0507]

Chemistry 41

[0508]

[0509] Example 12 Synthesis of 2,8-bis(2-(4-n-butylphenyl)ethyl)anthraquinone[1,2-b:5,6-b']dithiophene (Compound 11) (Step C2)

[0510] In a nitrogen atmosphere, 194 mg (1.42 mmol) of zinc chloride (Fujifilm Wako Pure Chemical Industries, Ltd.) and 4 mL of THF (Fujifilm Wako Pure Chemical Industries, Ltd., dehydrated grade) were added to a 50 mL Schlenk tube, and stirred under ice cooling. 4.5 mL (0.90 mmol) of a 0.2 M 2-(4-butylphenyl)ethylmagnesium bromide / THF solution synthesized in Synthesis Example 12 was added under ice cooling, and stirred at 0°C for 30 minutes, and then at room temperature for 16 hours to prepare a zinc reagent solution.

[0511] On the other hand, 39.7 mg (0.0886 mmol) of 2,8-dibromoanthraquinone [1,2-b: 5,6-b'] dithiophene (Compound 20) synthesized in Synthesis Example 23 and 7.96 mg (0.0109 mmol) of [1,1'-bis (diphenylphosphino) ferrocene] dichloropalladium (II) (Sigma-Aldrich) and 3 mL of THF (Fujifilm Wako Pure Chemical Industries, Ltd., dehydrated grade) were added to a 100 mL Schlenk tube. The previously prepared zinc reagent solution was added dropwise using a Teflon (registered trademark) cannula and stirred at room temperature for 24 hours. The reaction mixture was ice-cooled, 1 M hydrochloric acid was added, and toluene was added to separate the phases. The organic phase was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane as a solvent: toluene = 1 / 0 to 5 / 1). The obtained solid was rinsed with methanol and purified by recrystallization from hexane / toluene = 6 / 5 to obtain 12.6 mg (yield 23%) of 2,8-di(2-(4-n-butylphenyl)ethyl)anthraquinone[1,2-b:5,6-b′]dithiophene (Compound 11) as a yellow solid.

[0512] 1 H NMR (CDCl3): δ=8.59(s,2H), 7.85(d,J=8.7Hz,2H), 7.69(d,J=8.9Hz,2H), 7.19(d,J=8.0Hz,2H), 7.15(s,2H), 7.13(d,J=8.0 Hz, 2H), 3.32 (t, J = 7.5 Hz, 4H), 3.12 (t, J = 8.5 Hz, 4H), 2.61 (t, J = 7.6 Hz, 4H), 1.61 (m, 4H), 1.37 (m, 4H), 0.94 (t, J = 7.3 Hz, 6H).

[0513] Melting point: 227℃

[0514] (Compound 11)

[0515]

Chemistry 42

[0516]

[0517] Example 13 Synthesis of 2-(2-(4-n-butylphenyl)ethyl)anthraquinone[1,2-b:5,6-b']dithiophene (Compound 17) (Step C2)

[0518] The other component obtained by silica gel column chromatography in Example 12 was purified by recrystallization from hexane to obtain 5.8 mg (yield 15%) of yellow solid 2-(2-(4-n-butylphenyl)ethyl)anthraquinone[1,2-b:5,6-b′]dithiophene (Compound 17).

[0519] 1 H NMR (CDCl3): δ=8.70(s,1H), 8.62(s,1H), 7.89(d,J=8.5Hz,1H), 7.87(d,J=8.0Hz,1H), 7 .82(d,J=8.8Hz,1H), 7.71(d,J=8.8Hz,1H), 7.54(d,J=5.4Hz,1H), 7.49(d,J=5.1Hz,1H) , 7.19(d,J=8.0Hz,2H), 7.16(s,1H), 7.13(d,J=8.1Hz,2H), 3.32(t,J=7.4Hz,2H), 3.12( t,J=8.6Hz,2H), 2.61(t,J=7.7Hz,2H), 1.60(m,2H), 1.37(m,2H), 0.94(t,J=7.3Hz,3H).

[0520] Melting point: 161°C

[0521] (Compound 17)

[0522]

Chemistry 43

[0523]

[0524] Example 14 Synthesis of 2,8-bis(2-(4-n-heptylphenyl)ethyl)anthraquinone[1,2-b:5,6-b']dithiophene (Compound 12) (Step C2)

[0525] In a nitrogen atmosphere, 124 mg (0.909 mmol) of zinc chloride (Fujifilm Wako Pure Chemical Industries, Ltd.) and 2 mL of THF (Fujifilm Wako Pure Chemical Industries, Ltd., dehydrated grade) were added to a 50 mL Schlenk tube, and stirred under ice cooling. 3.4 mL (0.68 mmol) of a 0.2 M 2-(4-heptylphenyl)ethylmagnesium bromide / THF solution synthesized in Synthesis Example 15 was added under ice cooling, and stirred at 0°C for 20 minutes, and then stirred at room temperature for 16 hours to prepare a zinc reagent solution.

[0526] On the other hand, 31.4 mg (0.0701 mmol) of 2,8-dibromoanthraquinone[1,2-b:5,6-b']dithiophene (Compound 20) synthesized in Synthesis Example 23 and 5.20 mg (0.00711 mmol) of [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (Sigma-Aldrich) and 3 mL of THF (Fujifilm Wako Pure Chemical Industries, Ltd., dehydrated grade) were added to a 100 mL Schlenk tube. The previously prepared zinc reagent solution was added dropwise thereto using a Teflon (registered trademark) cannula, stirred at room temperature for 90 minutes, and then stirred at 50°C for 1 hour. The reaction mixture was ice-cooled, 1 M hydrochloric acid was added, and toluene was added to separate the phases. The organic phase was washed with water, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the obtained solid was rinsed and washed with methanol. The obtained residue was purified by silica gel column chromatography (hexane as a solvent: toluene = 1 / 0 to 5 / 1). The obtained solid was rinsed with methanol and purified by recrystallization from hexane / toluene = 5 / 4 to obtain 3.5 mg (yield 7%) of 2,8-di(2-(4-n-heptylphenyl)ethyl)anthraquinone[1,2-b:5,6-b′]dithiophene (Compound 12) as a yellow solid.

[0527] 1 H NMR (CDCl3): δ=8.59(s,2H), 7.85(d,J=9.0Hz,2H), 7.69(d,J=8.8Hz,2H), 7.19(d,J=7.9Hz,2H), 7.15(s,2H), 7.13(d,J=8.0H z, 2H), 3.32 (t, J = 7.6Hz, 4H), 3.11 (t, J = 8.5Hz, 4H), 2.59 (t, J = 7.6Hz, 4H), 1.61 (m, 4H), 1.29 (m, 16H), 0.89 (t, J = 6.5Hz, 6H).

[0528] (Compound 12)

[0529]

Chemistry 44

[0530]

[0531] Example 15 Synthesis of 2-(2-(4-n-heptylphenyl)ethyl)anthraquinone[1,2-b:5,6-b']dithiophene (Compound 18) (Step C2)

[0532] The other component obtained by silica gel column chromatography in Example 14 was purified by recrystallization from hexane to obtain 3.5 mg (yield 10%) of yellow solid 2-(2-(4-n-heptylphenyl)ethyl)anthraquinone[1,2-b:5,6-b′]dithiophene (Compound 18).

[0533] 1 H NMR (CDCl3): δ=8.70(s,1H), 8.62(s,1H), 7.90(d,J=8.5Hz,1H), 7.88(d,J=8.0Hz,1H), 7 .82(d,J=8.9Hz,1H), 7.71(d,J=8.9Hz,1H), 7.54(d,J=5.4Hz,1H), 7.49(d,J=5.1Hz,1H) , 7.19(d,J=8.0Hz,2H), 7.16(s,1H), 7.13(d,J=8.2Hz,2H), 3.32(t,J=7.7Hz,2H), 3.12( t,J=8.4Hz,2H), 2.59(t,J=7.5Hz,2H), 1.61(m,4H), 1.29(m,8H), 0.89(t,J=6.8Hz,3H).

[0534] (Compound 18)

[0535]

Chemistry 45

[0536]

[0537] Synthesis Example 24 Synthesis of Bromodithiophene Biphenylene Derivative (Compound 21) (Step A3)

[0538] In a nitrogen atmosphere, 126 mg (0.476 mmol) of a dithienyl biphenylene derivative (compound 2 in the publication) synthesized by the method described in Japanese Patent Application Laid-Open No. 2018-174322 and 15 ml of THF (Fujifilm Wako Pure Chemical Industries, Ltd., dehydrated grade) were added to a 50 ml Schlenk reaction vessel. The mixture was cooled to -78°C, 0.30 mL (0.480 mmol) of 1.6 M n-butyl lithium (Tokyo Chemical Industry Co., Ltd.) was added, and after stirring at -78°C for 15 minutes, it was stirred at room temperature for 30 minutes. After cooling to -78°C, 6 mL of a THF solution of 186 mg (0.571 mmol) of 1,2-dibromotetrachloroethane (Fujifilm Wako Pure Chemical Industries, Ltd., dehydrated grade) was added, and the mixture was stirred while warming to room temperature. After ice cooling, water was added to stop the reaction, and toluene was added to separate the phases. The organic phase was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (solvent: hexane) and recrystallized from hexane to obtain 85.1 mg (yield 47%) of a bromodithienylbiphenylene derivative (Compound 21) as a yellow solid.

[0539] 1H NMR (CDCl3): δ=7.23(d,J=7.1Hz,1H), 7.21(d,J=5.4Hz,1H), 7.05(d,J=5.8Hz,2H), 7.04(s,1H), 6.71(d,J=7.5Hz,1H), 6.67(d,J=7.3Hz,1H).

[0540] Example 16 Synthesis of 2-(2-phenylethyl)dithienyl biphenylene (Compound 13) (Step C3)

[0541] In a nitrogen atmosphere, 118 mg (0.866 mmol) of zinc chloride (Fujifilm Wako Pure Chemical Industries, Ltd.) and 2 mL of THF (Fujifilm Wako Pure Chemical Industries, Ltd., dehydrated grade) were added to a 50 mL Schlenk tube, and stirred under ice cooling. Under ice cooling, 1.90 mL (0.760 mmol) of a 0.4 M 2-phenylethylmagnesium bromide / THF solution synthesized in Synthesis Example 2 was added, and stirred at 0°C for 30 minutes and at room temperature for 14 hours to prepare a zinc reagent solution.

[0542] On the other hand, 36.2 mg (0.105 mmol) of the bromodithiophene biphenylene derivative synthesized in Synthesis Example 24, 10.1 mg (0.0138 mmol) of [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (Sigma-Aldrich), and 5 mL of THF (Fujifilm Wako Pure Chemical Industries, Ltd., dehydrated grade) were added to a 50 mL Schlenk tube. The previously prepared zinc reagent solution was added dropwise using a Teflon (registered trademark) cannula, and stirred at room temperature for 5 hours. The reaction mixture was ice-cooled, 1 M hydrochloric acid was added, and toluene was added to separate the phases. The organic phase was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (solvent: hexane). The resulting solid was rinsed and washed with methanol to obtain 15.1 mg (yield 39%) of a yellow solid of 2-(2-phenylethyl)dithiophene biphenylene (compound 13).

[0543] 1 H NMR (CDCl3): δ=7.30(m,2H), 7.21-7.18(m,5H), 7.04(d,J=5.6Hz,1H), 7.01(d,J=7.5Hz,1H), 6.71 (d,J=7.3Hz,1H), 6.69(s,1H), 6.66(d,J=7.3Hz,1H), 3.12(t,J=6.4Hz,2H), 3.03(t,J=6.4Hz,2H).

[0544] Melting point: 161°C

[0545] (Compound 13)

[0546]

Chemistry 46

[0547]

[0548] Synthesis Example 25 Synthesis of 1-(2-bromoethyl)-4-methylbenzene

[0549] In a nitrogen atmosphere, 5.36 g (39.3 mmol) of 2-(p-tolyl)ethanol (Tokyo Chemical Industry) and 80 ml of dichloromethane (Fujifilm Wako Pure Chemical Industries, Ltd., dehydrated grade) were added to a 100 ml two-necked flask. The solution was ice-cooled, 4.00 ml (42.1 mmol) of phosphorus tribromide was added, and after stirring for 30 minutes, stirring was continued at room temperature for 21 hours. The reaction solution was poured into ice, neutralized with a saturated sodium bicarbonate aqueous solution, and then dichloromethane was added to separate the phases. The organic phase was washed with a saturated sodium bicarbonate aqueous solution and water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (solvent: dichloromethane) to obtain 4.05 g (yield 52%) of a colorless liquid of 1-(2-bromoethyl)-4-methylbenzene.

[0550] 1 H NMR (CDCl3): δ=7.15(d,J=8.2Hz,2H), 7.11(d,J=8.2Hz,2H), 3.56(t,J=7.7Hz,2H), 3.14(t,J=7.7Hz,2H), 2.35(s,3H).

[0551] Synthesis Example 26 Synthesis of 2-(4-methylphenyl)ethylmagnesium bromide (Step B1)

[0552] In a nitrogen atmosphere, 228 mg (9.36 mmol) of magnesium (Fujifilm Wako Pure Chemical Industries, Ltd., crumbs) was added to a 50 mL two-necked flask, and the mixture was stirred under vacuum for 1 hour. In a nitrogen atmosphere, 20 mL of a THF (Fujifilm Wako Pure Chemical Industries, Ltd., dehydrated grade) solution of 1.60 g (8.02 mmol) of 1-(2-bromoethyl)-4-methylbenzene synthesized in Synthesis Example 25 was added, and the mixture was stirred at room temperature for 90 minutes. The solid was removed by filtration, thereby obtaining a 0.4 M 2-(4-methylphenyl)ethylmagnesium bromide / THF solution.

[0553] Example 17 Synthesis of 2-(2-(4-methylphenyl)ethyl)dithienylbiphenylene (Compound 14) (Step C3)

[0554] In a nitrogen atmosphere, 114 mg (0.836 mmol) of zinc chloride (Fujifilm Wako Pure Chemical Industries, Ltd.) and 2 mL of THF (Fujifilm Wako Pure Chemical Industries, Ltd., dehydrated grade) were added to a 50 mL Schlenk tube, and stirred under ice cooling. Under ice cooling, 1.80 mL (0.720 mmol) of a 0.4 M 2-(4-methylphenyl)ethylmagnesium bromide / THF solution synthesized in Synthesis Example 26 was added, and stirred at 0°C for 15 minutes and at room temperature for 14 hours to prepare a zinc reagent solution.

[0555] On the other hand, 24.4 mg (0.0711 mmol) of the bromodithiophene biphenylene derivative synthesized in Synthesis Example 24, 9.00 mg (0.0123 mmol) of [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (Sigma-Aldrich), and 7 mL of THF (Fujifilm Wako Pure Chemical Industries, Ltd., dehydrated grade) were added to a 50 mL Schlenk tube. The previously prepared zinc reagent solution was added dropwise using a Teflon (registered trademark) cannula, and stirred at room temperature for 5 hours. The reaction mixture was ice-cooled, 1 M hydrochloric acid was added, and toluene was added to separate the phases. The organic phase was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (solvent: hexane). The resulting solid was rinsed and washed with methanol to obtain 4.9 mg (yield 18%) of a yellow solid of 2-(2-(4-methylphenyl)ethyl)dithiophene biphenylene (Compound 14).

[0556] 1 H NMR (CDCl3): δ=7.20 (d, J=8.3Hz, 1H), 7.19 (d, J=5.4Hz, 1H), 7.04 (d, J=5.5Hz, 1H), 7.01 (d, J=7.4Hz, 1H), 6.71 (d, J = 7.3Hz, 1H), 6.69 (s, 1H), 6.66 (d, J = 7.4Hz, 1H), 3.09 (t, J = 7.0Hz, 2H), 2.99 (t, J = 7.8Hz, 2H), 2.33 (s, 3H).

[0557] Melting point: 151°C

[0558] (Compound 14)

[0559]

Chemistry 47

[0560]

[0561] Synthesis Example 27 Synthesis of 2-bromoanthra[1,2-b:5,6-b']dithiophene (Compound 22) (Step A-4)

[0562] In a nitrogen atmosphere, 481 mg (1.66 mmol) of anthra[1,2-b:5,6-b']dithiophene (Compound 19) synthesized in Synthesis Example 22 and 57 ml of THF (Fujifilm Wako Pure Chemical Industries, Ltd., dehydrated grade) were added to a 100 ml Schlenk reaction vessel. The mixture was cooled to -78°C, 1.05 mL (1.68 mmol) of 1.6 M n-butyl lithium (Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was stirred at -78°C for 2 hours. After cooling to -78°C, 24 mL of a THF solution of 634 mg (1.95 mmol) of 1,2-dibromotetrachloroethane (Fujifilm Wako Pure Chemical Industries, Ltd., dehydrated grade) was added, and the mixture was stirred while warming to room temperature. After ice cooling, water was added to stop the reaction, and toluene was added to separate the phases. The organic phase was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (solvent: hexane:toluene = 1 / 0 to 2 / 1) and recrystallized from toluene to obtain 372 mg (yield 51%) of 2-bromoanthra[1,2-b:5,6-b′]dithiophene (Compound 22) as a yellow solid.

[0563] 1 H NMR (CDCl3): δ = 8.70 (s, 1H), 8.56 (s, 1H), 7.90-7.86 (m, 3H), 7.71 (d, J = 8.7Hz, 1H), 7.57 (d, J = 5.0Hz, 1H), 7.50 (d, J = 5.4Hz, 1H), 7.48 (s, 1H).

[0564] Example 18 Synthesis of 2-(2-(4-methylphenyl)ethyl)anthraquinone[1,2-b:5,6-b']dithiophene (Compound 16) (Step C4)

[0565] In a nitrogen atmosphere, 207 mg (1.51 mmol) of zinc chloride (Fujifilm Wako Pure Chemical Industries, Ltd.) and 4 mL of THF (Fujifilm Wako Pure Chemical Industries, Ltd., dehydrated grade) were added to a 50 mL Schlenk tube, and stirred under ice cooling. Under ice cooling, 2.50 mL (1.00 mmol) of a 0.4 M 2-(4-methylphenyl)ethylmagnesium bromide / THF solution synthesized in Synthesis Example 26 was added, and stirred at 0°C for 30 minutes and at room temperature for 14 hours to prepare a zinc reagent solution.

[0566] On the other hand, 50.1 mg (0.136 mmol) of 2-bromoanthraquinone [1,2-b:5,6-b'] dithiophene (Compound 22) synthesized in Synthesis Example 27 and 11.0 mg (0.0150 mmol) of [1,1'-bis (diphenylphosphino) ferrocene] dichloropalladium (II) (Sigma-Aldrich) and 7 mL of THF (Fujifilm Wako Pure Chemical Industries, Ltd., dehydrated grade) were added to a 50 mL Schlenk tube. The previously prepared zinc reagent solution was added dropwise using a Teflon (registered trademark) cannula, and stirred at room temperature for 24 hours. The reaction mixture was ice-cooled, 1 M hydrochloric acid was added, and toluene was added to separate the phases. The organic phase was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane as a solvent: toluene = 1 / 0 to 10 / 1). The obtained solid was purified by recrystallization from hexane / toluene = 5 / 1 to obtain 13.8 mg (yield 30%) of 2-(2-(4-methylphenyl)ethyl)anthraquinone[1,2-b:5,6-b′]dithiophene (Compound 16) as a yellow solid.

[0567] 1 H NMR (CDCl3): δ=8.70(s,1H), 8.62(s,1H), 7.90(d,J=8.8Hz,1H), 7.87(d,J=8.8Hz,1H), 7.82(d,J=8.7Hz,1H), 7.71(d,J=8.8Hz, 1H), 7.54(d,J=5.4Hz,1H), 7.49(d,J=5.1Hz,1H), 7.18-7.12(m,5H), 3.32(t,J=7.7Hz,2H), 3.12(t,J=7.4Hz,2H), 2.35(s,3H).

[0568] Melting point: 190℃

[0569] (Compound 16)

[0570]

Chemistry 48

[0571]

[0572] Synthesis Example 28 Synthesis of 1,5-bis(trimethylsilylethynyl)-2,6-difluorobiphenylene (Step D1)

[0573] Under nitrogen atmosphere, 260 mg (0.591 mmol) of 2,6-difluoro-1,5-diiodobiphenylene synthesized by the method described in Japanese Patent Application Laid-Open No. 2018-174322, 10.3 mg (0.0146 mmol) of bis(triphenylphosphine)palladium dichloride (Fujifilm Wako Pure Chemical Industries, Ltd.), 5.2 mg (0.0273 mmol) of copper (I) iodide (Fujifilm Wako Pure Chemical Industries, Ltd.), 6 mL of toluene, and 6 ml of triethylamine were added to a 50 mL Schlenk reaction vessel. 174 mg (1.77 mmol) of trimethylsilyl acetylene (Tokyo Chemical Industry Co., Ltd.) was added to the resulting mixture, and stirred at 30°C for 6 hours. Water was added to the resulting reaction mixture to quench the reaction. The organic phase was extracted with toluene, washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (solvent: hexane:toluene = 1 / 0 to 20 / 1) to obtain 188 mg (yield 84%) of the target product as a light yellow solid.

[0574] 1 H NMR (CDCl3): δ=6.57 (dd, J=7.3Hz, 4.0Hz, 2H), 6.42 (dd,J=11.0Hz, 7.4Hz, 2H), 0.26 (s, 18H).

[0575] Synthesis Example 29 Synthesis of diphenylene [2,1-b: 6,5-b'] dithiophene (Step E1)

[0576] Under a nitrogen atmosphere, 133 mg (0.349 mmol) of 1,5-bis(trimethylsilylethynyl)-2,6-difluorobiphenylene synthesized in Synthesis Example 28, 301 mg (1.25 mmol) of sodium sulfide 9 hydrate (Sigma-Aldrich) and 8 ml of DMSO (Fujifilm Wako Pure Chemical Industries, Ltd.) were added to a 100 mL Schlenk reaction vessel. The mixture was heated to 90°C and stirred for 4 hours. After the resulting reaction mixture was cooled to 0°C, water and toluene were added. Extract with hot toluene, separate the phases, and wash the organic phase with water. The organic phase was concentrated under reduced pressure to obtain 78 mg (yield 84%) of a yellow solid of diphenylene [2,1-b:6,5-b'] dithiophene.

[0577] 1 H NMR (CDCl3): δ=7.31(d,J=5.7Hz,2H), 7.18(d,J=7.6H), 6.94(d,J=5.6Hz,2H), 6.65(d,J=7.4,2H).

[0578] Synthesis Example 30 Synthesis of 2,7-dibromobiphenyl[2,1-b:6,5-b']dithiophene (Step F1)

[0579] In a nitrogen atmosphere, 105 mg (0.397 mmol) of diphenylene [2,1-b:6,5-b'] dithiophene synthesized in Synthesis Example 29 and 9 ml of THF (Fujifilm Wako Pure Chemical Industries, Ltd., dehydrated grade) were added to a 100 ml Schlenk reaction vessel. The mixture was cooled to -78°C, 0.94 mL (1.50 mmol) of 1.6 M n-butyl lithium (Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was stirred at -78°C for 10 minutes. After stirring at 20°C for 25 minutes, the mixture was cooled to -78°C, 3 mL of a THF solution of 555 mg (1.70 mmol) of 1,2-dibromotetrachloroethane (Fujifilm Wako Pure Chemical Industries, Ltd., dehydrated grade) was added, and the mixture was stirred while warming to room temperature. After ice cooling, water was added to stop the reaction. Hexane was added to the precipitated solid and filtered with filter paper. The solid was washed with water, methanol and hexane, and the obtained residue was dried to obtain 86 mg (yield 51%) of 2,7-dibromobiphenyleno[2,1-b:6,5-b′]dithiophene as an orange-red solid.

[0580] 1 H NMR (CDCl3, 58° C.): δ = 7.02 (d, J = 7.7 Hz, 2H), 6.96 (s, 2H), δ = 6.58 (d, J = 7.7 Hz, 2H).

[0581] Example 19 Synthesis of 2,7-bis(2-phenylethyl)dithiophene biphenylene (Compound 9) (Step G1)

[0582] In a nitrogen atmosphere, 150 mg (1.10 mmol) of zinc chloride (Fujifilm Wako Pure Chemical Industries, Ltd.) and 7 mL of THF (Fujifilm Wako Pure Chemical Industries, Ltd., dehydrated grade) were added to a 50 mL Schlenk tube and stirred under ice-cooling. Under ice-cooling, 1.4 mL (0.56 mmol) of a 0.4 M 2-phenylethylmagnesium bromide / THF solution synthesized in Synthesis Example 2 was added, and the mixture was stirred at room temperature for 1 hour to prepare a zinc reagent solution. 45.4 mg (0.107 mmol) of 2,7-dibromobiphenylene [2,1-b:6,5-b'] dithiophene synthesized in Synthesis Example 30 and 3.30 mg (0.00451 mmol) of [1,1'-bis(diphenylphosphino)ferrocene] dichloropalladium (II) (Sigma-Aldrich) were added thereto. The mixture was stirred at 40°C for 13 hours. The reaction mixture was ice-cooled, 1 M hydrochloric acid was added, and toluene was added to separate the phases. The organic phase was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (solvent: hexane: toluene = 1 / 0 to 3 / 1). The solid was recrystallized from heptane / toluene = 1 / 2 to obtain 26 mg (yield 51%) of a yellow solid aromatic compound (Compound 9).

[0583] 1 H NMR (CDCl3): δ=7.34-7.20(m,10H), 7.04(d,J=7.6Hz,2H), 6.61(s,2H), 6.63(d,J=7.4Hz,2H), δ=3.11(t,J=8.64Hz,4H), δ=3.03(t,J=8.4Hz,4H).

[0584] (Compound 9)

[0585]

Chemistry 49

[0586]

[0587] Example 20 (Preparation of a solution for forming an organic semiconductor layer)

[0588] A solution for forming an organic semiconductor layer was prepared in the same manner as in Example 2 except that 0.44 mg of 2,7-bis(2-(4-propylphenyl)ethyl)dithienylene (Compound 4) synthesized in Example 5 was used. The solution was maintained at 25° C. after 10 hours (the concentration of Compound 4 was 0.10% by weight), and it was confirmed to be a compound suitable for film formation by drop casting and ink jetting.

[0589] Example 21 (Manufacturing of organic semiconductor layer and organic thin film transistor)

[0590] Using the organic semiconductor layer forming solution obtained in Example 20, and using the materials and film forming methods of the respective constituent members described in Example 3, a bottom gate-bottom contact type p-type organic thin film transistor was produced.

[0591] The transfer characteristics of the transistor element were evaluated and the hole carrier mobility was 1.86 cm 2 / V·second, the current switching ratio is 1.1×10 6 .

[0592] Furthermore, the organic thin film transistor was annealed at 130°C for 10 minutes, and then its electrical characteristics were measured. The carrier mobility of holes was 1.70 cm 2 / V·second, the current switching ratio is 1.0×10 6 , almost no performance degradation due to heat treatment was found.

[0593] Example 22 (Manufacturing of organic semiconductor layer and organic thin film transistor)

[0594] In air, 0.87 mg of 2,7-bis(2-(4-propylphenyl)ethyl)dithiophene biphenylene (Compound 4) synthesized in Example 5 and 440 mg of anisole (Sigma-Aldrich) were added to a 10 ml sample tube, and heated at 60°C to prepare a 0.20 wt% solution of Compound 4. Using the obtained solution, a bottom-gate-bottom-contact p-type organic thin film transistor was prepared using the materials and film-forming methods of the various components shown in Example 3.

[0595] The transfer characteristics of the transistor element were evaluated and the carrier mobility of holes was 2.48 cm 2 / V·second, the current switching ratio is 1.6×10 6 .

[0596] Furthermore, the organic thin film transistor was annealed at 130°C for 10 minutes, and then its electrical characteristics were measured. The carrier mobility of holes was 2.40 cm 2 / V·second, the current switching ratio is 1.4×10 6 , almost no performance degradation due to heat treatment was found.

[0597] Example 23 (Preparation of a solution for forming an organic semiconductor layer)

[0598] A solution for forming an organic semiconductor layer was prepared in the same manner as in Example 2 except that 1.74 mg of 2,7-di(2-(4-butylphenyl)ethyl)dithienylene (Compound 5) synthesized in Example 6 was used. The solution was maintained at 25° C. after 10 hours (the concentration of Compound 5 was 0.40% by weight), and it was confirmed to be a compound suitable for film formation by drop casting and ink jetting.

[0599] Example 24 (Preparation of a solution for forming an organic semiconductor layer)

[0600] A solution for forming an organic semiconductor layer was prepared in the same manner as in Example 2 except that 0.87 mg of 2,7-di(2-(4-heptylphenyl)ethyl)dithienyl biphenylene (Compound 6) synthesized in Example 7 was used. The solution was maintained at 25° C. after 10 hours (the concentration of Compound 6 was 0.20% by weight), and it was confirmed to be a compound suitable for film formation by drop casting and ink jetting.

[0601] Example 25 (Manufacturing of organic semiconductor layer and organic thin film transistor)

[0602] Using the organic semiconductor layer forming solution obtained in Example 24, and using the materials and film forming methods of the respective constituent members described in Example 3, a bottom gate-bottom contact type p-type organic thin film transistor was produced.

[0603] The transfer characteristics of the transistor element were evaluated and the hole carrier mobility was 1.19 cm 2 / V·second, the current switching ratio is 1.1×10 6 .

[0604] Furthermore, the organic thin film transistor was annealed at 130°C for 10 minutes, and then its electrical characteristics were measured. The carrier mobility of holes was 1.15 cm 2 / V·second, the current switching ratio is 1.0×10 6 , almost no performance degradation due to heat treatment was found.

[0605] Example 26 (Preparation of a solution for forming an organic semiconductor layer)

[0606] A solution for forming an organic semiconductor layer was prepared in the same manner as in Example 2 except that 0.87 mg of 2,8-di(2-phenylethyl)anthraquinone[1,2-b:5,6-b']dithiophene (Compound 10) synthesized in Example 10 was used. The solution was maintained at 25° C. after 10 hours (the concentration of Compound 10 was 0.20% by weight), and it was confirmed to be a compound suitable for film formation by drop casting and ink jetting.

[0607] Example 27 (Preparation of a Solution for Forming an Organic Semiconductor Layer)

[0608] A solution for forming an organic semiconductor layer was prepared in the same manner as in Example 2 except that 4.35 mg of 2-(2-phenylethyl)dithienyl biphenylene (Compound 13) synthesized in Example 16 was used. The solution was maintained at 25° C. after 10 hours (the concentration of Compound 13 was 1.00 wt%), and it was confirmed to be a compound suitable for film formation by drop casting and ink jetting.

[0609] Example 28 (Preparation of a solution for forming an organic semiconductor layer)

[0610] A solution for forming an organic semiconductor layer was prepared in the same manner as in Example 2 except that 4.35 mg of 2-(2-(4-methylphenyl)ethyl)dithienylene (Compound 14) synthesized in Example 17 was used. The solution was maintained at 25° C. after 10 hours (the concentration of Compound 14 was 1.00% by weight), and it was confirmed to be a compound suitable for film formation by drop casting and ink jetting.

[0611] Example 29 (Preparation of a Solution for Forming an Organic Semiconductor Layer)

[0612] A solution for forming an organic semiconductor layer was prepared in the same manner as in Example 2 except that 1.74 mg of 2-(2-phenylethyl)anthraquinone[1,2-b:5,6-b']dithiophene (Compound 15) synthesized in Example 11 was used. The solution was maintained at 25°C for 10 hours (the concentration of Compound 15 was 0.40 wt%), and it was confirmed to be a compound suitable for film formation by drop casting and ink jetting.

[0613] Example 30 (Preparation of a solution for forming an organic semiconductor layer)

[0614] A solution for forming an organic semiconductor layer was prepared in the same manner as in Example 2 except that 2.18 mg of 2-(2-(4-methylphenyl)ethyl)anthraquinone[1,2-b:5,6-b']dithiophene (Compound 16) synthesized in Example 18 was used. The solution was maintained at 25°C for 10 hours (the concentration of Compound 16 was 0.50 wt%), and it was confirmed to be a compound suitable for film formation by drop casting and ink jetting.

[0615] Example 31 (Preparation of a Solution for Forming an Organic Semiconductor Layer)

[0616] A solution for forming an organic semiconductor layer was prepared in the same manner as in Example 2 except that 4.35 mg of 2-(2-(4-n-butylphenyl)ethyl)anthraquinone[1,2-b:5,6-b']dithiophene (Compound 17) synthesized in Example 13 was used. The solution was maintained at 25° C. after 10 hours (the concentration of Compound 17 was 1.00% by weight), and it was confirmed to be a compound suitable for film formation by drop casting and ink jetting.

[0617] Example 32 (Manufacturing of organic semiconductor layer and organic thin film transistor)

[0618] A solution for forming an organic semiconductor layer (the concentration of compound 17 is 0.20 wt %) was prepared by the same method as in Example 2 except that 0.87 mg of 2-(2-(4-n-butylphenyl)ethyl)anthraquinone[1,2-b:5,6-b']dithiophene (Compound 17) synthesized in Example 13 was used. Using the obtained solution for forming an organic semiconductor layer, the materials and film forming methods of the various components shown in Example 3 were used to prepare a bottom-gate-bottom-contact p-type organic thin film transistor.

[0619] The transfer characteristics of the transistor element were evaluated and the hole carrier mobility was 1.13 cm 2 / V·second, the current switching ratio is 8.1×10 7 .

[0620] Furthermore, the organic thin film transistor was annealed at 130°C for 10 minutes, and then its electrical characteristics were measured. The carrier mobility of holes was 1.10 cm 2 / V·second, the current switching ratio is 8.0×10 7 , almost no performance degradation due to heat treatment was found.

[0621] Example 33 (Preparation of a solution for forming an organic semiconductor layer)

[0622] A solution for forming an organic semiconductor layer was prepared in the same manner as in Example 2 except that 0.87 mg of 2-(2-(4-n-heptylphenyl)ethyl)anthraquinone[1,2-b:5,6-b']dithiophene (Compound 18) synthesized in Example 15 was used. The solution was maintained at 25° C. after 10 hours (the concentration of Compound 18 was 0.20% by weight), and it was confirmed to be a compound suitable for film formation by drop casting and ink jetting.

[0623] Synthesis Example 31 Synthesis of 4-propoxyphenylethanol

[0624] In a 300 ml Schlenk reaction vessel under a nitrogen atmosphere, 4.51 g (21.0 mmol) of 1-bromo-4-propoxybenzene (Tokyo Chemical Industry) and 80 ml of THF (Fujifilm Wako Pure Chemical Industries, dehydrated grade) were added. The mixture was cooled to -78°C, 22.0 mL (35.0 mmol) of 1.6 M n-butyl lithium (Tokyo Chemical Industry) was added, and the mixture was stirred at -78°C for 2 hours. 25.0 ml (30.0 mmol) of 1.2 M ethylene oxide THF solution (Tokyo Chemical Industry) was added at -78°C, and the mixture was stirred while warming to room temperature. After adding 1 M hydrochloric acid, diethyl ether was added to separate the phases. The organic phase was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (solvent: dichloromethane, ethyl acetate) to obtain 2.83 g (yield 64%) of a colorless liquid of 4-propoxyphenylethanol.

[0625] 1 H NMR (CDCl3): δ = 7.13 (dd, J = 1.9Hz, 6.4Hz, 2H), 6.85 (dd, J = 2.1Hz, 6.4Hz, 2H), 3.91 (t, J = 6.7Hz, 2H) , 3.82(t,J=6.7Hz,2H), 2.81(t,J=6.6Hz,2H), 1.81(tq,J=6.6Hz,7.4Hz,2H), 1.04(t,J=7.4Hz,3H).

[0626] Synthesis Example 32 Synthesis of 1-(2-bromoethyl)-4-propoxybenzene

[0627] In a nitrogen atmosphere, 2.83 g (15.7 mmol) of 4-propoxyphenethanol synthesized in Synthesis Example 31 and 20 ml of toluene (Fujifilm Wako Pure Chemical Industries, Ltd., dehydrated grade) were added to a 100 ml eggplant-shaped bottle. 0.80 ml (8.4 mmol) of phosphorus tribromide was added at room temperature, and the mixture was stirred for 20 minutes, and then stirred at 100°C for 4 hours. The reaction solution was poured into ice, neutralized with a saturated sodium bicarbonate aqueous solution, and then dichloromethane was added to separate the phases. The organic phase was washed with a saturated sodium bicarbonate aqueous solution and water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (solvent: dichloromethane) to obtain 3.40 g (yield 84%) of a colorless liquid of 1-(2-bromoethyl)-4-propoxybenzene.

[0628] 1 H NMR (CDCl3): δ=7.11(d,J=8.4Hz,2H), 6.86(d,J=8.6Hz,2H), 3.91(t,J=6.6Hz,2H), 3.53(t ,J=7.4Hz,2H), 3.10(t,J=7.6Hz,2H), 1.82(tq,J=6.8Hz,7.4Hz,2H), 1.04(t,J=7.4Hz,3H).

[0629] Synthesis Example 33 Synthesis of 2-(4-propoxyphenyl)ethylmagnesium bromide (Step B1)

[0630] In a nitrogen atmosphere, 172 mg (7.06 mmol) of magnesium (Fujifilm Wako Pure Chemical Industries, Ltd., crumbs) was added to a 20 mL two-necked flask, and the mixture was stirred under vacuum for 1 hour. In a nitrogen atmosphere, 15 mL of a THF (Fujifilm Wako Pure Chemical Industries, Ltd., dehydrated grade) solution of 1.46 g (6.00 mmol) of 1-(2-bromoethyl)-4-propoxybenzene synthesized in Synthesis Example 32 was added, and the mixture was stirred at room temperature for 1 hour. The solid was removed by filtration to obtain a 0.4 M 2-(4-propoxyphenyl)ethylmagnesium bromide / THF solution.

[0631] Example 34 Synthesis of 2-(2-(4-propoxyphenyl)ethyl)anthraquinone[1,2-b:5,6-b']dithiophene (Compound 23) (Step C4)

[0632] In a nitrogen atmosphere, 149 mg (1.10 mmol) of zinc chloride (Fujifilm Wako Pure Chemical Industries, Ltd.) and 2 mL of THF (Fujifilm Wako Pure Chemical Industries, Ltd., dehydrated grade) were added to a 50 mL Schlenk tube, and stirred under ice cooling. Under ice cooling, 1.80 mL (0.72 mmol) of a 0.4 M 2-(4-propoxyphenyl)ethylmagnesium bromide / THF solution synthesized in Synthesis Example 33 was added, and stirred at 0°C for 15 minutes and at room temperature for 15 hours to prepare a zinc reagent solution.

[0633] On the other hand, 50.6 mg (0.144 mmol) of 2-bromoanthraquinone [1,2-b:5,6-b'] dithiophene (Compound 22) synthesized in Synthesis Example 27 and 6.6 mg (0.0090 mmol) of [1,1'-bis (diphenylphosphino) ferrocene] dichloropalladium (II) (Sigma-Aldrich) and 5 mL of THF (Fujifilm Wako Pure Chemical Industries, Ltd., dehydrated grade) were added to a 50 mL Schlenk tube. The previously prepared zinc reagent solution was added dropwise using a Teflon (registered trademark) cannula and stirred at room temperature for 24 hours. The reaction mixture was ice-cooled, 1 M hydrochloric acid was added, and toluene was added to separate the phases. The organic phase was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane as solvent: toluene = 1 / 0 to 2 / 5). The obtained solid was purified by recrystallization from hexane / toluene = 10 / 3 to obtain 8.5 mg (yield 13%) of 2-(2-(4-propoxyphenyl)ethyl)anthraquinone[1,2-b:5,6-b′]dithiophene (Compound 23) as a yellow solid.

[0634] 1 H NMR (CDCl3): δ=8.69(s,1H), 8.62(s,1H), 7.90(d,J=9.1Hz,1H), 7.87(d,J=9.2Hz,1H), 7. 82(d,J=8.9Hz,1H), 7.71(d,J=8.8Hz,1H), 7.54(d,J=5.0Hz,1H), 7.49(d,J=5.1Hz,1H), 7 .17(d,J=8.6Hz,1H), 7.14(s,1H), 6.86(d,J=8.7Hz,1H), 3.92(t,J=6.4Hz,2H), 3.30(t,J =7.6Hz, 2H), 3.10 (t, J = 7.5Hz, 2H), 1.81 (tq, J = 7.5Hz, 7.6Hz, 2H), 1.04 (t, J = 7.5Hz, 3H).

[0635] Melting point: 181°C

[0636] (Compound 23)

[0637]

Chemistry 50

[0638]

[0639] Synthesis Example 34 Synthesis of 2-(4-methoxyphenyl)ethylmagnesium bromide (Step B1)

[0640] In a nitrogen atmosphere, 161 mg (6.61 mmol) of magnesium (Fujifilm Wako Pure Chemical Industries, Ltd., crumbs) was added to a 20 mL two-necked flask, and the mixture was stirred under vacuum for 1 hour. In a nitrogen atmosphere, 15 mL of a THF (Fujifilm Wako Pure Chemical Industries, Ltd., dehydrated grade) solution of 1.29 g (6.00 mmol) of 4-methoxyphenethyl bromide (Sigma-Aldrich) was added, and the mixture was stirred at room temperature for 1 hour. The solid was removed by filtration to obtain a 0.4 M 2-(4-methoxyphenyl)ethylmagnesium bromide / THF solution.

[0641] Example 35 Synthesis of 2-(2-(4-methoxyphenyl)ethyl)anthraquinone[1,2-b:5,6-b']dithiophene (Compound 24) (Step C4)

[0642] In a nitrogen atmosphere, 125 mg (0.914 mmol) of zinc chloride (Fujifilm Wako Pure Chemical Industries, Ltd.) and 2 mL of THF (Fujifilm Wako Pure Chemical Industries, Ltd., dehydrated grade) were added to a 50 mL Schlenk tube, and stirred under ice cooling. Under ice cooling, 1.60 mL (0.640 mmol) of a 0.4 M 2-(4-methoxyphenyl)ethylmagnesium bromide / THF solution synthesized in Synthesis Example 34 was added, and stirred at 0°C for 15 minutes and at room temperature for 15 hours to prepare a zinc reagent solution.

[0643] On the other hand, 50.4 mg (0.136 mmol) of 2-bromoanthraquinone [1,2-b:5,6-b'] dithiophene (Compound 22) synthesized in Synthesis Example 27 and 7.8 mg (0.011 mmol) of [1,1'-bis (diphenylphosphino) ferrocene] dichloropalladium (II) (Sigma-Aldrich) and 5 mL of THF (Fujifilm Wako Pure Chemical Industries, Ltd., dehydrated grade) were added to a 50 mL Schlenk tube. The previously prepared zinc reagent solution was added dropwise using a Teflon (registered trademark) cannula and stirred at room temperature for 24 hours. The reaction mixture was ice-cooled, 1 M hydrochloric acid was added, and toluene was added to separate the phases. The organic phase was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane as solvent: toluene = 1 / 0 to 2 / 5). The obtained solid was purified by recrystallization from hexane / toluene = 3 / 2 to obtain 17.8 mg (yield 31%) of 2-(2-(4-methoxyphenyl)ethyl)anthraquinone[1,2-b:5,6-b′]dithiophene (Compound 24) as a yellow solid.

[0644] 1H NMR (CDCl3): δ=8.70(s,1H), 8.62(s,1H), 7.90(d,J=9.2Hz,1H), 7.87(d,J=9.2Hz,1H), 7.82(d,J=8.7Hz,1H), 7.71(d,J=8.7Hz,1H), 7.54(d,J=5.3 Hz,1H), 7.49(d,J=5.1Hz,1H), 7.18(d,J=8.6Hz,1H), 7.14(s,1H), 6.86(d ,J=8.6Hz,1H), 3.81(s,3H), 3.30(t,J=7.5Hz,2H), 3.09(t,J=7.5Hz,2H).

[0645] Melting point: 231°C

[0646] (Compound 24)

[0647]

Chemistry 51

[0648]

[0649] Example 36 (Preparation of a solution for forming an organic semiconductor layer)

[0650] A solution for forming an organic semiconductor layer was prepared in the same manner as in Example 2 except that 4.35 mg of 2-(2-(4-propoxyphenyl)ethyl)anthraquinone[1,2-b:5,6-b']dithiophene (Compound 23) synthesized in Example 34 was used. The solution was maintained at 25°C for 10 hours (the concentration of Compound 23 was 1.00 wt%), and it was confirmed to be a compound suitable for film formation by drop casting and ink jetting.

[0651] Example 37 (Preparation of a solution for forming an organic semiconductor layer)

[0652] A solution for forming an organic semiconductor layer was prepared in the same manner as in Example 2 except that 0.44 mg of 2-(2-(4-methoxyphenyl)ethyl)anthraquinone[1,2-b:5,6-b']dithiophene (Compound 24) synthesized in Example 35 was used. The solution was maintained at 25° C. after 10 hours (the concentration of Compound 24 was 0.10% by weight), and it was confirmed to be a compound suitable for film formation by drop casting and ink jetting.

[0653] Comparative Example 1

[0654] (Preparation of Solution for Forming Organic Semiconductor Layer)

[0655] In air, 0.44 mg of 2,7-diphenyl[1]benzothieno[3,2-b][1]benzothiophene (Sigma-Aldrich) and 434 mg of toluene (Fujifilm Wako Pure Chemical Industries, pure grade) were added to a 10 ml sample tube, heated to 50°C, and left to cool at room temperature (25°C). Solid precipitation was confirmed, and due to its low solubility, it was confirmed that this compound was not suitable for film formation by drop casting and inkjet.

[0656] Comparative Example 2

[0657] (Preparation of Solution for Forming Organic Semiconductor Layer)

[0658] In air, a solution for forming an organic semiconductor layer was prepared in a 10 ml sample tube using 2,7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene (Sigma-Aldrich) by the same method as in Example 2. After 10 hours at 25°C, the solution (0.20 wt%) was maintained, confirming that the compound was suitable for film formation by drop casting and ink jetting.

[0659] (Manufacturing of organic semiconductor layers and organic thin film transistors)

[0660] Using this organic semiconductor layer-forming solution, a thin film of 2,7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene was prepared in the same manner as in Example 4 to produce a bottom-gate-bottom-contact p-type organic thin film transistor.

[0661] The transfer characteristics of the transistor element were evaluated and the carrier mobility of holes was 1.02 cm 2 / V·second, the current switching ratio is 3.0×10 5 .

[0662] Furthermore, the organic thin film transistor was annealed at 130°C for 10 minutes, and then its electrical properties were measured. As a result, the transistor could not be operated, and it was found that the thermal treatment caused a significant decrease in performance. Microscopic observation confirmed that the organic semiconductor layer was destroyed by heating.

[0663] Comparative Example 3

[0664] (Preparation of Solution for Forming Organic Semiconductor Layer)

[0665] In air, a 10 ml sample tube was charged with 2,7-di(n-octyl)dithiophene biphenylene described in Japanese Patent Application Laid-Open No. 2018-174322 (Compound 3 in the publication) to prepare a solution for forming an organic semiconductor layer by the same method as in Example 2. After 10 hours at 25° C., the solution state (0.20% by weight) was maintained, confirming that the compound was suitable for film formation by drop casting and ink jetting.

[0666] (Manufacturing of organic semiconductor layers and organic thin film transistors)

[0667] Using this organic semiconductor layer-forming solution and the materials and film-forming methods of the respective constituent members described in Example 3, a top-gate-bottom-contact p-type organic thin-film transistor was produced.

[0668] The transfer characteristics of the transistor element were evaluated and the hole carrier mobility was 0.60 cm 2 / V·second, the current switching ratio is 3.0×10 6 .

[0669] Comparative Example 4

[0670] (Preparation of Solution for Forming Organic Semiconductor Layer)

[0671] In air, a solution for forming an organic semiconductor layer was prepared in a 10 ml sample tube using 2,8-dioctylanthraquinone[1,2-b:5,6-b']dithiophene synthesized in Synthesis Example 6 by the same method as in Example 2. After 10 hours at 25°C, the solution state (0.20 wt%) was maintained, confirming that the compound was suitable for film formation by drop casting and ink jetting.

[0672] (Manufacturing of organic semiconductor layers and organic thin film transistors)

[0673] This organic semiconductor layer-forming solution was used, and the materials of the respective components and the film-forming method described in Example 3 were used. However, a thin film could not be formed, and a top-gate-bottom-contact p-type organic thin-film transistor could not be produced.

[0674] Industrial applicability

[0675] The aromatic compound of the present invention can achieve high carrier mobility and is excellent in heat resistance and solubility, and therefore can be expected to be used in semiconductor device materials represented by organic thin film transistors.

[0676] Description of Reference Numerals

[0677] (A): Bottom-gate-top-contact organic thin film transistor

[0678] (B): Bottom-gate-bottom-contact organic thin film transistor

[0679] (C): Top-gate-top-contact organic thin film transistor

[0680] (D): Top-gate-bottom-contact organic thin film transistor

[0681] 1: Organic semiconductor layer

[0682] 2: Substrate

[0683] 3: Gate

[0684] 4: Gate insulation layer

[0685] 5: Source

[0686] 6: Drain

Claims

1. An aromatic compound, which is a compound represented by the following formula (5) or the following formula (5-2): ； In formula (5) or (5-2), R 25 ~R 28 Among the combinations of two adjacent components in , only one group constitutes the following formula (6), and in the combination of R 29 ~R 32 Among the combinations of two adjacent groups in the formula (6), only one group constitutes the following formula (6-2), each forming a 5-membered ring; R that does not constitute the following formula (6) and the following formula (6-2) 25 ~R 32 and R 69 , R 70 Each independently represents a hydrogen atom, ； In formula (6), X 7 represents a sulfur atom; Y 4 Represents CR 37 ; R 37 Represents a hydrogen atom; R 33 is a group represented by the following formula (2); ； In formula (6-2), X 7 , Y 4 , R 37 represents X in the above formula (6) 7 , Y 4 , R 37 Same meaning; R 33b represents one selected from a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a group represented by the following formula (2); ； In formula (2), A represents an aryl group having 6 to 26 carbon atoms; l and n each independently represent 0 or 1; m represents an integer of 1 to 20; Z 1 , Z 2 Represents a hydrogen atom.

2. The aromatic compound according to claim 1, wherein Among the aromatic compounds represented by formula (5) or formula (5-2), formula (6-2) is the following formula (6-3): ； In formula (6-3), X 7 , Y 4 , R 37 represents X in the above formula (6) 7 , Y 4 , R 37 Same meaning; R 33c Represents a hydrogen atom.

3. The aromatic compound according to claim 1, wherein Among the aromatic compounds represented by formula (5) or formula (5-2), formula (6-2) is the following formula (6-4): ； In formula (6-4), X 7 , Y 4 , R 37 represents X in the above formula (6) 7 , Y 4 , R 37 Same meaning; R 33d It is a group represented by the above formula (2).

4. The aromatic compound according to claim 1, wherein The compound represented by formula (5) or formula (5-2) is a compound represented by one of the following formulas (7-1) to (7-5): ； In formulas (7-1) to (7-5), X 8 , X 9 Each independently represents a sulfur atom; Y 5 , Y 6 Each independently represents CR 45 ; R 39 ~R 40 , R 42 ~R 43 , R 45 , R 71 , R 72 Each independently represents a hydrogen atom, R 38 and R 41 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a group represented by the formula (2), R 38 and R 41 At least one of them is a group represented by the formula (2).

5. The aromatic compound according to claim 4, wherein The compound represented by formula (5) or formula (5-2) is a compound represented by formula (7-1), formula (7-2), or formula (7-5).

6. The aromatic compound according to claim 4 or 5, wherein R 38 and R 41 Each independently represents one selected from the group represented by the formula (2) and a hydrogen atom; R 39 , R 40 , R 42 ~R 43 , R 45 , R 71 , R 72 A hydrogen atom.

7. The aromatic compound according to claim 4 or 5, wherein R 38 and R 41 is a group represented by the formula (2), R 39 , R 40 , R 42 ~ R 43 , R 45 , R 71 , R 72 A hydrogen atom. 8 . A solution for forming an organic semiconductor layer, comprising the aromatic compound according to claim 1 . 9 . An organic semiconductor layer comprising the aromatic compound according to claim 1 . 10 . An organic thin film transistor comprising the organic semiconductor layer according to claim 9 .

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